Conjugated diene polymer and rubber composition

Abstract

The present invention relates to: a conjugated diene-based polymer in which physical properties other than processability of the conjugated diene-based polymer are maintained at the level of a highly linear conjugated diene-based polymer by introducing a branched chain into the linear conjugated diene-based polymer, thus exhibiting improved processability while maintaining mixing properties in the rubber composition at a high level; and a rubber composition containing the conjugated diene-based polymer.

Description

Technical Field

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS]

[0002] This application claims the benefit of Korean Patent Application No. 10-2023-0149216 filed on November 1, 2023, in the Korean Intellectual Property Office, the contents of which are incorporated herein by reference.

[0003] The present invention relates to a conjugated diene polymer and a rubber composition containing the same. Background Art

[0004] Recently, with the increasing interest in energy conservation and environmental issues, there is a need to improve the fuel efficiency of automobiles. As one of the methods to achieve this demand, a method of increasing the cis bond content and linearity of polybutadiene in a rubber composition for forming tires while narrowing the molecular weight distribution has been proposed.

[0005] Polybutadiene can be prepared using a Ziegler-Natta catalyst prepared by activating an organic acid metal compound with an alkylaluminum and a halogenated alkylaluminum compound, and reacting the prepared catalyst with a 1,3-butadiene monomer to prepare polybutadiene.

[0006] Here, the organic acid metal compound includes titanium compounds, nickel compounds, cobalt compounds and lanthanum compounds, and lanthanide rare earth element compounds are mainly used from the viewpoint of increasing the cis bond content and linearity of polybutadiene while narrowing the molecular weight distribution.

[0007] Representative examples of lanthanide rare earth element compounds include neodymium compounds, with a specific example including NdV (neodymium versatate). The lanthanide rare earth element compound is alkylated with an alkylaluminum compound, and then activated by halogenation with a haloalkylaluminum compound. To stabilize the catalyst, 1,3-butadiene monomer is added during the alkylation reaction for pre-forming.

[0008] However, polybutadiene prepared by a catalyst prepared using a lanthanide rare earth element compound, particularly a neodymium-based compound, has high physical properties but high linearity and thus poor processability.

[0009] [Prior art literature]

[0010] [Patent Document]

[0011] (Patent Document 1) US 9056303 B2 Summary of the Invention

[0012] Technical issues

[0013] The task to be solved in the present invention is to improve the processing performance while maintaining the physical properties of the conjugated diene polymer at the level of high linear polybutadiene.

[0014] That is, in order to solve the task mentioned in the background of the present invention, the present invention aims to provide a conjugated diene polymer that maintains the physical properties of the conjugated diene polymer other than the processing performance at the level of a high linear conjugated diene polymer, thereby improving the processing performance while maintaining the mixing performance in the rubber composition at a high level.

[0015] Furthermore, the present invention aims to provide a rubber composition comprising the conjugated diene-based polymer.

[0016] Technical Solution

[0017] In order to achieve the above-mentioned objectives, the present invention provides a conjugated diene polymer and a rubber composition.

[0018] (1) The present invention provides a conjugated diene polymer comprising conjugated diene monomer units, having a cis bond content of 95.0 wt % or more, and having a difference (Max-Min) between the maximum and minimum phase angles of 2.3° or more as determined by dynamic viscoelasticity analysis based on frequency variation within an angular frequency range of 0.01 rad / s to 100 rad / s.

[0019] (2) The present invention provides a conjugated diene polymer according to (1), wherein, when dynamic viscoelasticity analysis is performed based on frequency change, the maximum value (Max) of the phase angle confirmed within the angular frequency range of 0.01 rad / s to 100 rad / s is 44° or less.

[0020] (3) The present invention provides a conjugated diene polymer according to (1) or (2), wherein, when dynamic viscoelasticity analysis is performed based on frequency variation, the difference between the phase angle at an angular frequency of 1 rad / s and the phase angle at an angular frequency of 0.1 rad / s (PA@1rad / s-PA@0.1rad / s) is greater than +1.7°.

[0021] (4) The present invention provides the conjugated diene polymer according to any one of (1) to (3), wherein, when dynamic viscoelasticity analysis is performed based on frequency change, the complex viscosity at an angular frequency of 0.01 rad / s is 180,000 Pa·s or more.

[0022] (5) The present invention provides the conjugated diene polymer according to any one of (1) to (4), wherein the conjugated diene polymer includes a branched chain.

[0023] (6) The present invention provides the conjugated diene-based polymer according to any one of (1) to (5), wherein the number average molecular weight is 200,000 g / mol to 400,000 g / mol.

[0024] (7) The present invention provides the conjugated diene polymer according to any one of (1) to (6), wherein the weight average molecular weight is 500,000 g / mol to 800,000 g / mol.

[0025] (8) The present invention provides the conjugated diene polymer according to any one of (1) to (7), wherein the molecular weight distribution is 2.0 to 3.0.

[0026] (9) The present invention provides a conjugated diene polymer according to any one of (1) to (9), wherein the Mooney viscosity (ML1+4@100°C) is 40 to 65.

[0027] (10) The present invention provides a rubber composition comprising the conjugated diene polymer according to any one of (1) to (9).

[0028] Beneficial effects

[0029] The conjugated diene polymer of the present invention maintains the physical properties of the conjugated diene polymer other than the processability at the level of a high linear conjugated diene polymer by introducing a branched chain into the linear conjugated diene polymer, thereby showing improved processability while maintaining the mixing performance in the rubber composition at a high level. DETAILED DESCRIPTION

[0030] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0031] It should be understood that the words or terms used in the present disclosure and claims should not be interpreted as having the meanings defined in commonly used dictionaries. Based on the principle that the inventor can appropriately define the meanings of words or terms to best explain the present invention, words or terms should be interpreted as having meanings consistent with their meanings in the technical concept of the present invention.

[0032] Measurement method

[0033] In this specification, "1,4-cis bond content (wt%)" is the content of cis-1,4 bonds in the conjugated diene portion measured by Fourier transform infrared spectroscopy (FT-IR). Using carbon disulfide in the same cell as a blank, the FT-IR transmission spectrum of a carbon disulfide solution of a conjugated diene polymer prepared at a concentration of 5 mg / mL was measured, and the FT-IR transmission spectrum of about 1130 cm-1 of the measured spectrum was used. -1 The maximum peak (a, baseline), about 967 cm indicating the trans-1,4 bond-1 The minimum peak (b) at about 911 cm indicating vinyl bonds -1 The minimum peak (c) and the peak at about 736 cm indicating the cis-1,4 bond -1 The minimum peak (d) of each content was obtained.

[0034] In this specification, the "Mooney viscosity (ML1+4, @100°C)" is measured using a Monsanto MV2000E large rotor at a rotor speed of 2±0.02 rpm at 100°C after the polymer is placed at room temperature (23±3°C) for more than 30 minutes, 27±3 g is collected and filled into the mold cavity, and torque is applied by operating the pressure plate.

[0035] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (MWD) were measured using gel permeation chromatography (GPC) after dissolving the polymer in tetrahydrofuran (THF) at 40°C for 30 minutes. In this case, two PLgelOlexis columns and one PLgelmixed-C column from Polymer Laboratories were used in combination. In addition, all newly replaced columns used a mixed bed type column, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

[0036] In this specification, frequency-dependent viscoelastic analysis was measured using a DHR-2 rheometer from TA Instruments and 8 mm diameter parallel plates at 120° C., 0.1% strain, and an angular frequency range of 0.01 to 100 rad / s.

[0037] Conjugated diene polymers

[0038] The present invention provides a conjugated diene-based polymer having improved processability characteristics while maintaining the excellent physical properties of highly linear conjugated diene-based polymers in terms of tensile properties, viscoelasticity, and wear resistance.

[0039] According to one embodiment of the present invention, the conjugated diene polymer may be a linear conjugated diene polymer into which a branch is introduced. In this case, the branch is formed without adding a monomer, a modifier, or the like containing the branch. In the present invention, the branch is defined based on the viscoelasticity analysis results according to the following frequency change.

[0040] According to one embodiment of the present invention, the conjugated diene polymer contains conjugated diene monomer units, has a cis bond content of 95.0 wt % or more, and has a difference (Max-Min) between the maximum and minimum values ​​of the phase angle confirmed in the angular frequency range of 0.01 rad / s to 100 rad / s of 2.3° or more if dynamic viscoelasticity analysis is performed according to the change in frequency.

[0041] Polybutadiene is usually prepared by polymerizing 1,3-butadiene monomer using a Ziegler-Natta catalyst, which is prepared by activating an organic acid metal compound with an aluminum alkyl and a haloalkyl aluminum compound. Here, lanthanum rare earth element compounds, such as neodymium compounds, are widely used as one of organic acid metal compounds. After the alkylation reaction using the aluminum alkyl compound, the organic acid metal compound is activated by a halogenation reaction using a haloalkyl aluminum compound, and in order to stabilize the catalyst, 1,3-butadiene monomer is sometimes added during the alkylation reaction to preform. However, polybutadiene prepared by catalysts prepared using lanthanum rare earth element compounds, particularly neodymium compounds, has high compounding properties such as tensile properties, viscoelasticity and wear resistance, but suffers from a problem of relatively poor compounding processability due to high linearity.

[0042] The conjugated diene polymer according to the present invention is prepared using a lanthanide rare earth element compound as a main catalyst. By controlling the catalyst composition and polymerization conditions, branches are introduced into the structure of the polymer chain formed by polymerization, thereby maintaining the excellent compounding properties originally exhibited by high linearity, such as tensile properties, viscoelasticity, and wear resistance, while improving compounding processability. According to one embodiment of the present invention, the conjugated diene polymer may include conjugated diene monomer units, have a cis bond content of 95.0% by weight or greater, and, when subjected to dynamic viscoelasticity analysis based on frequency changes, have a phase angle difference (Max-Min) of 2.3° or greater, as determined within an angular frequency range of 0.01 rad / s to 100 rad / s.

[0043] Specifically, the conjugated diene polymer has 95.0 wt % or more, 95.1 wt % or more, 95.2 wt % or more, 95.3 wt % or more, 95.4 wt % or more, 95.5 wt % or more, 95.6 wt % or more, 95.7 wt % or more, 95.8 wt % or more, 95.9 wt % or more, 96.0 wt % or more, 96.1 wt % or more, 96.2 wt % or more, 96.3 wt % or more, 96.4 wt % or more. % or more, 96.5 wt % or more, 96.6 wt % or more, 96.7 wt % or more, 96.8 wt % or more, 96.9 wt % or more, 97.0 wt % or more, 97.1 wt % or more, 97.2 wt % or more, 97.3 wt % or more, 97.4 wt % or more, or 97.5 wt % or more of 1,4-cis bond content, and can also be 100.0 wt % or less, 99.5 wt % or less, or 99.0 wt % or less.

[0044] In addition, if the conjugated diene polymer is subjected to dynamic viscoelasticity analysis according to frequency change, the conjugated diene polymer may have a difference (Max-Min) between the maximum and minimum values ​​of the phase angle confirmed in the angular frequency range of 0.01 rad / s to 100 rad / s of 2.3° or more, 2.35° or more, or 2.40° or more, and 3.5° or less, 3.30° or less, or 3.10° or less.

[0045] Furthermore, according to one embodiment of the present invention, when a dynamic viscoelasticity analysis based on frequency change is performed on a conjugated diene polymer, the maximum value (Max) of the phase angle confirmed within an angular frequency range of 0.01 rad / s to 100 rad / s may be 44° or less. Specifically, the maximum value (Max) of the phase angle may be 44° or less or 43.5° or less, and 38° or more, 38.5° or more, or 39° or more.

[0046] In addition, if a dynamic viscoelastic analysis of a conjugated diene polymer is performed according to frequency variation, the difference between the phase angle at an angular frequency of 1 rad / s and the phase angle at 0.1 rad / s (PA@1rad / s-PA@0.1rad / s) may be +1.7° or more. Here, PA@1rad / s and PA@0.1rad / s represent PA at 1 rad / s and PA at 0.1 rad / s, respectively. Specifically, the phase angle difference (PA@1rad / s-PA@0.1rad / s) may be +1.71° or more or +1.73° or more, and +3.50° or less, +3.00° or less, or +2.90° or less.

[0047] According to one embodiment of the present invention, when a frequency-dependent dynamic viscoelasticity analysis is performed on a conjugated diene polymer, the complex viscosity at an angular frequency of 0.01 rad / s may be 180,000 Pa.s or greater. Specifically, the complex viscosity may be 180,000 Pa.s to 500,000 Pa.s, or 180,000 Pa.s to 300,000 Pa.s.

[0048] The difference between the maximum and minimum phase angles (Max-Min), the phase angle difference (PA@1 rad / s - PA@0.1 rad / s), and the complex viscosity vary depending on the branch lengths in the conjugated diene polymer. As the branch lengths increase, the difference between the maximum and minimum phase angles (Max-Min) and the phase angle difference (PA@1 rad / s - PA@0.1 rad / s) increase. Furthermore, the complex viscosity at low angular frequencies (0.01 rad / s) tends to increase, while the complex viscosity at high angular frequencies (1.0 rad / s) tends to decrease.

[0049] In one embodiment of the present invention, the copolymer polymer can improve cold flow and processing performance by satisfying the difference between the maximum and minimum values ​​of the phase angle (Max-Min), the difference in phase angle (PA@lrad / s-PA@O.1rad / s) and the complex viscosity, and the conjugated diene polymer according to one embodiment of the present invention that satisfies the difference between the maximum and minimum values ​​of the phase angle (Max-Min), the difference in phase angle (PA@1rad / s-PA@O.1rad / s) and the complex viscosity can refer to a conjugated diene polymer that contains branches with appropriate lengths in an appropriate proportion in the polymer.

[0050] According to one embodiment of the present invention, the conjugated diene-based polymer provides a conjugated diene-based polymer including a branched chain.

[0051] According to one embodiment of the present invention, the conjugated diene polymer may include a conjugated diene monomer unit, wherein the conjugated diene monomer unit refers to a repeating unit formed by polymerization of a conjugated diene monomer.

[0052] According to one embodiment of the present invention, the conjugated diene polymer may comprise 80 wt % or more, 85 wt % or more, 90 wt % or more, 95 wt % or more or 100 wt % of 1,3-butadiene monomer units, and optionally 20 wt % or less, 15 wt % or less, 10 wt % or less or 5 wt % or less of other conjugated diene monomer units copolymerizable with the 1,3-butadiene monomer, and within this range, a reduction in the cis-1,4 bond content in the conjugated diene polymer can be prevented. The 1,3-butadiene monomer may be 1,3-butadiene or a derivative thereof, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene. Other conjugated diene monomers copolymerizable with 1,3-butadiene may be 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene.

[0053] According to one embodiment of the present invention, the conjugated diene polymer can be a conjugated diene polymer catalyzed by a catalyst composition comprising a lanthanide rare earth element compound. That is, the conjugated diene polymer can be a conjugated diene polymer comprising an organometallic portion activated by a catalyst composition comprising a neodymium compound.

[0054] According to one embodiment of the present invention, the conjugated diene polymer may have a number average molecular weight of 200,000 g / mol or more and 400,000 g / mol or less. Within this range, when applied to a rubber composition, the polymer exhibits excellent tensile properties and excellent processing properties, thereby improving the workability of the rubber composition and facilitating kneading, resulting in excellent mechanical properties and performance balance of the rubber composition.

[0055] According to one embodiment of the present invention, the conjugated diene polymer may have a weight average molecular weight of 500,000 g / mol or more and 800,000 g / mol or less. Within this range, when applied to a rubber composition, the tensile properties are excellent, and the processing properties are excellent, so that the workability of the rubber composition is improved, kneading is easy, and the mechanical properties and performance balance of the rubber composition are excellent.

[0056] According to one embodiment of the present invention, conjugated diene polymer can have more than 2.0 and less than 3.0 molecular weight distribution (Mw / Mn).Molecular weight distribution can be calculated by the ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn).In this case, number average molecular weight (Mn) is the common mean value of the single polymer molecular weight calculated by measuring the molecular weight of n polymer chains, obtaining the sum of molecular weight and dividing the sum by n, and weight average molecular weight (Mw) represents the molecular weight distribution of polymer composition.All molecular weight averages can be represented by grams per mole (g / mol).In addition, weight average molecular weight and number average molecular weight can each represent the polystyrene conversion molecular weight analyzed by gel permeation chromatography (GPC).

[0057] According to one embodiment of the present invention, if the conjugated diene polymer satisfies the molecular weight distribution, weight average molecular weight (Mw) and number average molecular weight conditions at the same time, then if applied to a rubber composition, the rubber composition has excellent tensile properties, viscoelasticity and processing properties, and the performance balance between them is excellent.

[0058] According to one embodiment of the present invention, the conjugated diene-based polymer may have a Mooney viscosity (ML1+4, @100°C) of 40 to 65. Here, @100°C means at 100°C.

[0059] Method for preparing conjugated diene polymer

[0060] The present invention provides a method for preparing a conjugated diene polymer. The method for preparing a conjugated diene polymer can be the method for preparing the above-mentioned conjugated diene polymer.

[0061] According to one embodiment of the present invention, the method for preparing a conjugated diene-based polymer may include a step of polymerizing a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a catalyst composition to prepare a living polymer ( S100 ).

[0062] According to one embodiment of the present invention, the catalyst composition may include a lanthanide rare earth element compound, an alkylating agent, a halide, and an organic solvent. In addition, the catalyst composition may include a reaction product of a lanthanide rare earth element compound, an alkylating agent, and a halide.

[0063] According to one embodiment of the present invention, the lanthanide rare earth element compound can be a neodymium compound, and specific examples thereof include: neodymium carboxylates (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.); organic phosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, bis(1- phosphonates (e.g., neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium disilylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, etc.); organic phosphinates (e.g., neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium disilylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, etc.); organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium Neodymium, neodymium octylphosphinate, neodymium (1-methylheptyl)phosphinate, neodymium (2-ethylhexyl)phosphinate) etc.); carbamates (e.g., neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, neodymium dibenzylcarbamate etc.); dithiocarbamates (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate etc. etc.); xanthates (e.g., neodymium methylxanthate, neodymium ethylxanthate, neodymium isopropylxanthate, neodymium butylxanthate, neodymium benzylxanthate, etc.); β-diketonates (e.g., neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylacetonate, etc.); alkoxides or allyl oxides (e.g., neodymium methoxide, neodymium ethoxide, neodymium isopropylate, neodymium phenoxide, neodymium nonylphenolate, etc.); halide or pseudohalide (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium thiocyanate, neodymium azide, etc.); halide oxide (for example, neodymium oxyfluoride, neodymium oxychloride, neodymium oxybromide, etc.); or organic neodymium compounds containing one or more rare earth element-carbon bonds (for example, Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn (cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln (allyl) 3, Ln (allyl) 2Cl, etc., wherein Ln is a rare earth metal element and R is a hydrocarbon group), and may include any one of them or a mixture of two or more of them.

[0064] According to one embodiment of the present invention, the lanthanide rare earth element compound may be a neodymium compound represented by Formula 1 below.

[0065] [Formula 1]

[0066]

[0067] In formula 1, R 1 to R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, but R 1 to R 3 In one embodiment, in Formula 1, R 1 It may be an alkyl group having 4 to 12 carbon atoms, R 2 and R 3 may each independently be hydrogen or an alkyl group having 2 to 8 carbon atoms, but R 2 and R 3 In a more specific embodiment, in Formula 1, R 1 It can be an alkyl group having 6 to 8 carbon atoms, R 2 and R 3 may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, but R 2 and R 3 Not all hydrogen.

[0068] According to one embodiment of the present invention, the lanthanide rare earth element compound may be one or more selected from the following: neodymium 2-ethylhexanoate (or neodymium versatate), neodymium 2,2-dimethyldecanoate, neodymium 2,2-diethyldecanoate, neodymium 2,2-dipropyldecanoate, neodymium 2,2-dibutyldecanoate, neodymium 2,2-dihexyldecanoate, neodymium 2,2-dioctyldecanoate, neodymium 2-ethyl-2-propyldecanoate, neodymium 2-ethyl-2-butyldecanoate, neodymium 2-ethyl-2-hexyldecanoate, neodymium 2-propyl-2-butyldecanoate, neodymium 2-propyl-2-hexyldecanoate , 2-propyl-2-isopropyldecanoate, neodymium 2-butyl-2-hexyldecanoate, neodymium 2-hexyl-2-octyldecanoate, neodymium 2,2-diethyloctanoate, neodymium 2,2-dipropyloctanoate, neodymium 2,2-dibutyloctanoate, neodymium 2,2-dihexyloctanoate, neodymium 2-ethyl-2-propyloctanoate, neodymium 2-ethyl-2-hexyloctanoate, neodymium 2,2-diethylnonanoate, neodymium 2,2-dipropylnonanoate, neodymium 2,2-dibutylnonanoate, neodymium 2,2-dihexylnonanoate, neodymium 2-ethyl-2-propylnonanoate and neodymium 2-ethyl-2-hexylnonanoate.

[0069] According to one embodiment of the present invention, a neodymium compound may contain a carboxylic acid ligand having an alkyl group of various lengths with two or more carbon atoms at the α-position. This induces spatial changes around the central neodymium metal, thereby blocking entanglement between the compounds. Consequently, when a conjugated diene polymer is polymerized using this catalyst composition, oligomerization is suppressed. Furthermore, this neodymium compound has high solubility in solvents, and the proportion of neodymium located in the central portion, which is difficult to convert into a catalytically active species, is reduced, resulting in a high conversion rate to the catalytically active species.

[0070] According to one embodiment of the present invention, the solubility of the neodymium compound at room temperature (25° C.) may be about 60 parts by weight or more relative to 100 parts by weight of the non-polar solvent. The solubility of the neodymium compound refers to the degree to which the neodymium compound dissolves clearly without turbidity, and by exhibiting such a high solubility, excellent catalytic activity can be exhibited.

[0071] According to one embodiment of the present invention, the alkylating agent is an organometallic compound capable of transferring a hydrocarbon group to another metal and can be used as a cocatalyst. The alkylating agent can be an organometallic compound that is soluble in the polymerization solvent and contains a metal-carbon bond, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound.

[0072] According to one embodiment of the present invention, the alkylating agent may be an organoaluminum compound, specific examples of which include: alkylaluminum, such as tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum; dihydrocarbylaluminum hydrides, such as diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, Phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydride; and hydrocarbylaluminum hydrides such as ethylaluminum hydride, n-propylaluminum hydride, isopropylaluminum hydride, n-butylaluminum hydride, isobutylaluminum hydride, and n-octylaluminum hydride.

[0073] According to one embodiment of the present invention, the alkylating agent may be an alkylaluminum compound represented by Formula 2 below.

[0074] [Formula 2]

[0075] AYR 4 R 5 R 6

[0076] In formula 2, R 4 to R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, but R 4 to R 6 It is not entirely hydrogen, and tri-n-hexyl aluminum and tri-n-octyl aluminum may not be included. In a specific embodiment, in Formula 2, R4 to R 6 may each independently be hydrogen or an alkyl group having 3 to 8 carbon atoms, but R 4 to R 6 In a more specific embodiment, in Formula 2, R 4 to R 6 may each independently be hydrogen or an alkyl group having 3 to 5 carbon atoms, but R 4 to R 6 Not entirely hydrogen.

[0077] According to one embodiment of the present invention, the alkylating agent may include two or more alkylaluminum compounds. In a specific embodiment, the alkylating agent may include two or more selected from dialkylaluminum hydrides and trialkylaluminums. In a more specific embodiment, the alkylating agent may include one or more dialkylaluminum hydrides and one or more trialkylaluminums. In a more specific embodiment, the alkylating agent may include diisobutylaluminum hydride and triisobutylaluminum, or diisobutylaluminum hydride and triethylaluminum.

[0078] According to one embodiment of the present invention, the catalyst composition can be obtained by introducing an alkylating agent at a molar ratio of 1 mol or more, 2 mol or more, 3 mol or more, 4 mol or more, 5 mol or more, 6 mol or more, 7 mol or more, 8 mol or more, 9 mol or more, 10 mol or more, 11 mol or more, 12 mol or more, 13 mol or more, 14 mol or more, or 15 mol or more relative to 1 mol of the lanthanide rare earth element compound, and can also include the alkylating agent at a molar ratio of 200 mol or less, 150 mol or less, 80 mol or less, 60 mol or less, 50 mol or less, 40 mol or less, 30 mol or less, or 25 mol or less.

[0079] According to one embodiment of the present invention, the halide may be a halogen single substance, an interhalogen compound, a hydrogen halide, an organic halide, a non-metallic halide, a metal halide or an organic metal halide.

[0080] According to one embodiment of the present invention, the halogen single species may be fluorine, chlorine, bromine or iodine.

[0081] According to one embodiment of the present invention, the interhalogen compound may be iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.

[0082] According to one embodiment of the present invention, the hydrogen halide may be hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide.

[0083] According to one embodiment of the present invention, the organic halide may be tert-butyl chloride (t-BuCl), tert-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chlorodiphenylmethane, bromodiphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzyl chloride, benzyl bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSC1), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also known as "iodoform"), tetraiodomethane, 1-iodopropane, 2-iodopropane, 1,3-diiodopropane, tert-butyl iodide, 2,2-dimethyl-1-iodopropane (also known as "neopentyl iodide"), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzyl iodide (also known as "benzylidene iodide"), trimethylsilyl iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, or methyl iodoformate.

[0084] According to one embodiment of the present invention, the non-metal halide can be phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl4), silicon tetrabromide, arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide or selenium tetraiodide.

[0085] According to one embodiment of the present invention, the metal halide can be tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetrachloride, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide or magnesium diiodide.

[0086] According to one embodiment of the present invention, the organometallic halide can be an alkylaluminum halide or an alkylaluminum sesquihalide. In a specific embodiment, the organometallic halide can be dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, sesquimethylaluminum chloride, sesquiethylaluminum chloride (EASC), sesquiisobutylaluminum chloride, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, dimethyltin chloride, trimethyl ... tert-Butyltin dichloride, di-tert-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide, methylmagnesium iodide, dimethylaluminum iodide, diethylaluminum iodide, di-n-butylaluminum iodide, diisobutylaluminum iodide, di-n-octylaluminum iodide, methylaluminum diiodide, ethylaluminum diiodide, n-butylaluminum diiodide, isobutylaluminum diiodide, sesquimethylaluminum iodide, sesquiethylaluminum iodide, sesquiisobutylaluminum iodide, ethylmagnesium iodide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin diiodide or di-tert-butyltin diiodide.

[0087] According to one embodiment of the present invention, from the viewpoint of improving catalytic activity and thus reactivity, the halide may be one or more selected from alkylaluminum halides represented by Formula 3 below and alkylaluminum sesquihalides represented by Formula 4 below.

[0088] [Formula 3]

[0089] AYR 7 R 8 R 9

[0090] In formula 3, R 7 to R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, but R 7 to R 9 In one embodiment, in Formula 3, R 7 to R 9 may each independently be a halogen group or an alkyl group having 1 to 6 carbon atoms, but R 7 to R 9 In a more specific embodiment, in Formula 3, R 7 and R 8 may be each independently an alkyl group having 1 to 4 carbon atoms, R 9It may be a halogen group.

[0091] [Formula 4]

[0092]

[0093] In formula 4, R 10 to R 12 Each of X1 to X3 may be independently an alkyl group having 1 to 12 carbon atoms, and each of X1 to X3 may be independently a halogen group. In a specific embodiment, in Formula 4, R 10 to R 12 Can be each independently an alkyl group having 1 to 6 carbon atoms. In a more specific embodiment, in Formula 4, R 10 to R 12 Each independently may be an alkyl group having 1 to 4 carbon atoms.

[0094] According to one embodiment of the present invention, the halide can be one or more selected from dialkylaluminum halides and sesquialkylaluminum halides, and the types of dialkylaluminum halides and sesquialkylaluminum halides are as described above. In a specific embodiment, the dialkylaluminum halide can be diethylaluminum chloride, and the sesquialkylaluminum halide can be sesquiethylaluminum chloride.

[0095] According to one embodiment of the present invention, the catalyst composition may contain the halide at a molar ratio of 0.1 mol or more, 0.5 mol or more, 1.0 mol or more, 1.5 mol or more, 2.0 mol or more, 2.5 mol or more, or 3.0 mol or more relative to 1 mol of the lanthanide rare earth element compound. In addition, the halide may be contained at a molar ratio of 20 mol or less, 15 mol or less, 10 mol or less, 8 mol or less, 6 mol or less, or 5 mol or less relative to 1 mol of the lanthanide rare earth element compound.

[0096] According to one embodiment of the present invention, the catalyst composition may include an organic solvent. The organic solvent may be a non-polar solvent that does not react with the components of the catalyst composition. In a specific embodiment, the organic solvent may be a straight chain, branched chain or cyclic aliphatic hydrocarbon with 5 to 20 carbon atoms, such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; a mixed solvent of aliphatic hydrocarbons with 5 to 20 carbon atoms, such as petroleum ether, petroleum spirit and kerosene; or an aromatic hydrocarbon solvent, such as benzene, toluene, ethylbenzene and xylene. In a more specific embodiment, the organic solvent may be a straight chain, branched chain or cyclic aliphatic hydrocarbon with 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, preferably n-hexane, cyclohexane or a mixture thereof.

[0097] Meanwhile, according to one embodiment of the present invention, the catalyst composition can be prepared by stirring a lanthanide rare earth element compound and a first alkylating agent in an organic solvent for pre-activation, adding a second alkylating agent thereto and stirring for alkylation, and then adding a halide for halogenation. Here, the first alkylating agent can be one or more selected from the above-mentioned trialkylaluminums, and the second alkylating agent can be any one or more selected from the above-mentioned dialkylaluminum hydrides. Pre-activation can be carried out by stirring at a temperature of 0°C to 40°C, alkylation can be carried out by stirring at a temperature of -10°C to 30°C, and halogenation can be carried out by stirring at a temperature of -20°C to 20°C.

[0098] When the catalyst composition is prepared under such conditions, the catalytic activity can be maximized, and in the case of polymerization of conjugated diene monomers, the polymerization of the monomers can proceed rapidly, thereby increasing the reaction between polymer chains, which can be beneficial to the ultimate preparation of conjugated diene monomers with appropriately introduced branches.

[0099] According to one embodiment of the present invention, the conjugated diene monomer that can be introduced in step (S100) can be one or more selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene and 2,4-hexadiene.

[0100] According to one embodiment of the present invention, the hydrocarbon solvent in step (S100) may be one or more selected from n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.

[0101] According to one embodiment of the present invention, the catalyst composition can be used in such an amount that the neodymium compound is 0.03 mmol or more, 0.04 mmol or more, 0.05 mmol or more, or 0.06 mmol or more relative to a total of 100 g of conjugated diene monomers, and can also be used in such an amount that the neodymium compound is 0.15 mmol or less, 0.14 mmol or less, 0.13 mmol or less, 0.12 mmol or less, 0.11 mmol or less, 0.10 mmol or less, 0.09 mmol or less, or 0.08 mmol or less.

[0102] According to one embodiment of the present invention, the polymerization in step (S100) can be carried out as continuous polymerization in a polymerization reactor comprising at least two reactors, or can be carried out in a batch reactor. In addition, the polymerization can be a temperature-raising polymerization, an isothermal polymerization or a constant temperature polymerization (adiabatic polymerization).

[0103] According to one embodiment of the present invention, constant temperature polymerization refers to polymerization by reaction heat itself without arbitrarily applying heat after the introduction of the catalyst composition, temperature-raising polymerization refers to increasing the temperature by arbitrarily applying heat after the introduction of the catalyst composition, and isothermal polymerization refers to adding heat or removing heat by applying heat to keep the temperature of the reactants constant after the introduction of the catalyst composition.

[0104] According to one embodiment of the present invention, the polymerization in step (S100) can be performed using coordinated anionic polymerization, and the polymerization environment can be bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization. A specific embodiment can be solution polymerization.

[0105] According to one embodiment of the present invention, the polymerization in step (S100) can be carried out at a temperature of above -20°C, above -10°C, above 0°C, above 10°C, above 20°C, above 30°C, above 40°C, above 50°C or above 60°C, and can be carried out at a temperature below 200°C, below 150°C, below 120°C or below 90°C. Within this range, the polymerization reaction can be smoothly controlled while ensuring the cis-1,4-bond content of the prepared conjugated diene polymer.

[0106] According to one embodiment of the present invention, the polymerization in step (S100) can be carried out for more than 15 minutes, more than 20 minutes, more than 30 minutes, more than 40 minutes, more than 50 minutes or more than 1 hour, and can be carried out for less than 3 hours, less than 2 hours and 30 minutes, or less than 2 hours.

[0107] As another embodiment, according to one embodiment of the present invention, the polymerization in step (S100) can be carried out by continuous polymerization using a continuous reactor in which two or more, or two to ten, or two to five, or two to four reactors are connected in series. In this case, it is more conducive to the preparation of the conjugated diene polymer with introduced branches having the above-mentioned characteristics.

[0108] In addition, according to one embodiment of the present invention, the polymerization in step (S100) can be carried out for more than 60 minutes, more than 70 minutes, more than 80 minutes, more than 90 minutes, or less than 180 minutes, less than 150 minutes, or less than 120 minutes. In this case, it is more conducive to the preparation of the conjugated diene polymer with introduced branches having the above-mentioned characteristics.

[0109] In addition, according to one embodiment of the present invention, the polymerization in step (S100) can be carried out by dividing the conjugated diene monomer into two or more parts. When the conjugated diene monomer is divided into two or more parts, the amount of the conjugated diene monomer added after the second part can be 20 to 40 parts by weight, or 25 to 35 parts by weight relative to 100 parts by weight of the total conjugated diene monomer added during the polymerization. In addition, when the conjugated diene monomer is divided into three or more parts, the respective amounts of the conjugated diene monomers added in the second, third, and nth parts can be added by appropriately allocating the amount of the conjugated diene monomer added after the second part.

[0110] In addition, if the conjugated diene monomer is introduced separately, the conjugated diene monomer introduced after the initial stage can be introduced at a time point when the polymerization conversion rate of the initially introduced conjugated diene monomer is 50% or more, 60% or more, or 70% or more, and 90% or less, 85% or less, or 80% or less.

[0111] According to one embodiment of the present invention, the conjugated diene-based polymer formed through the polymerization in step (S100) may be a living polymer including sites activated by the catalyst composition.

[0112] According to one embodiment of the present invention, a step of reacting the living polymer with a modifier ( S200 ) may be included. The modifier may be a known modifier that can be used when preparing a conjugated diene polymer using a catalyst composition containing a lanthanide rare earth element compound.

[0113] According to one embodiment of the present invention, the preparation method of the conjugated diene polymer may include the following steps: after preparing the active polymer, further using an additive such as a reaction terminator (such as polyoxyethylene glycol phosphate) or an antioxidant (such as 2,6-di-tert-butyl-p-cresol) for completing the polymerization reaction to terminate the polymerization. In addition, additives that promote solution polymerization, such as chelating agents, dispersants, pH regulators, deoxidizers or oxygen scavengers, may optionally be further used together with the reaction terminator.

[0114] The preparation method of the conjugated diene polymer according to one embodiment of the present invention can be carried out by appropriately selecting and combining the conditions in the above method, so that a conjugated diene polymer meeting the above parameters can be prepared, and specifically, the method can be carried out by appropriately selecting and controlling the catalyst composition preparation conditions, such as the preactivation step, polymerization time, monomer distribution, reactor temperature and catalyst addition amount, so that a conjugated diene polymer meeting the above parameters can be prepared.

[0115] Rubber composition

[0116] The present invention provides a rubber composition.

[0117] According to one embodiment of the present invention, the rubber composition may include a conjugated diene polymer. In a specific embodiment, the rubber composition may include the conjugated diene polymer in an amount of 0.1% by weight or more, 10% by weight or more, or 20% by weight or more, and may also include the conjugated diene polymer in an amount of 100% by weight or less, 95% by weight or less, or 90% by weight or less. Within this range, the wear resistance and crack resistance of a molded article, such as a tire, manufactured using the rubber composition can be sufficiently ensured.

[0118] According to one embodiment of the present invention, in addition to the conjugated diene polymer, the rubber composition may further include other rubber components as needed. In this case, the rubber component may be included in an amount of 90% by weight or less relative to the total weight of the rubber composition. Specifically, the rubber component may be included in an amount of 1% to 900% by weight relative to 100% by weight of the conjugated diene copolymer.

[0119] According to one embodiment of the present invention, the rubber component may be a natural rubber or a synthetic rubber, for example, the rubber component may be a natural rubber (NR), including cis-1,4-polyisoprene; a modified natural rubber, such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber, which are modified or purified from general natural rubber; or a synthetic rubber, such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, chloroprene rubber, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and any one of them or a mixture of two or more of them may be used.

[0120] According to one embodiment of the present invention, the rubber composition may have a difference between the Mooney viscosity (ML1+4@100°C) of the conjugated diene polymer and the Mooney viscosity (ML1+4@100°C) of the rubber composition of 30 or less. In a specific embodiment, the rubber composition may have a difference between the Mooney viscosity (ML1+4@100°C) of the conjugated diene polymer and the Mooney viscosity (ML1+4@100°C) of the rubber composition of 30 or less, 29 or less, 28 or less, 27 or less, 26 or less, 25 or less, 24 or less, 23 or less, 22 or less, 21 or less, or 20 or less. In addition, the lower limit is not particularly limited, but may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, 13 or more, 14 or more, or 15 or more. In this way, if the difference between the Mooney viscosity (ML1+4@100°C) of the conjugated diene-based polymer and the Mooney viscosity (ML1+4@100°C) of the rubber composition is adjusted within the above range, processability can be particularly improved.

[0121] According to one embodiment of the present invention, the rubber composition may have a Mooney viscosity (ML1+4 @ 100°C) of 50 or more and 100 or less. In a specific embodiment, the rubber composition may have a Mooney viscosity (ML1+4 @ 100°C) of 50 or more, 51 or more, 52 or more, 53 or more, 54 or more, 55 or more, 56 or more, 57 or more, 58 or more, 59 or more, 60 or more, or 61 or more, and 100 or less, 99 or less, 98 or less, 97 or less, 96 or less, 95 or less, 94 or less, 93 or less, 92 or less, 91 or less, 90 or less, 89 or less, 88 or less, 87 or less, 86 or less, 85 or less, or 84 or less. The Mooney viscosity of the rubber composition may vary depending on other components other than the conjugated diene polymer further contained in the rubber composition, but if controlled within this range, processability can be particularly improved.

[0122] According to one embodiment of the present invention, the rubber composition may include 20 parts by weight or more and 90 parts by weight or less of a filler relative to 100 parts by weight of the conjugated diene polymer. The filler may be a silica filler, a carbon black filler, or a combination thereof. In a specific embodiment, the filler may be a carbon black filler.

[0123] According to one embodiment of the present invention, the carbon black filler may have a thickness of 20 m 2 / g to 250m 2The carbon black filler may have a nitrogen adsorption specific surface area (N2SA, measured in accordance with JIS K 6217-2:2001) of 80 cc / 100 g / g. Within this range, the rubber composition can have excellent processability while sufficiently ensuring the reinforcing properties of the filler. Furthermore, the carbon black filler may have a dibutyl phthalate absorption value (DBP) of 80 cc / 100 g to 200 cc / 100 g. Within this range, the rubber composition can have excellent processability while sufficiently ensuring the reinforcing properties of the filler.

[0124] According to one embodiment of the present invention, the silica filler may be wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. In a specific embodiment, the silica filler may be wet silica, which has the most significant effect of improving fracture characteristics and achieving wet grip performance. In addition, the silica filler may have a particle size of 120 m 2 / g to 180m 2 / g nitrogen surface area per gram (N2SA) and 100m 2 / g to 200m 2 The cetyltrimethylammonium bromide (CTAB) adsorption surface area is 1.5 wt % / g, and within this range, the processability of the rubber composition can be excellent while sufficiently ensuring the reinforcing performance of the filler.

[0125] According to one embodiment of the present invention, if a silica-based filler is used as a filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation properties. The silane coupling agent may be bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide. In a specific embodiment, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide in consideration of the reinforcing property improvement effect.

[0126] According to one embodiment of the present invention, the rubber composition may be sulfur-crosslinkable and thus may further include a vulcanizing agent. The vulcanizing agent may specifically be sulfur powder, which may be included in an amount of 0.1 to 10 parts by weight relative to 100 parts by weight of the rubber component. Within this range, the elastic modulus and strength required for the vulcanized rubber composition can be ensured while ensuring low fuel consumption.

[0127] According to one embodiment of the present invention, in addition to the above components, the rubber composition may further include various additives commonly used in the rubber industry, specifically, vulcanization accelerators, processing oils, plasticizers, anti-aging agents, scorch retardants, zinc white, stearic acid, thermosetting resins or thermoplastic resins.

[0128] According to one embodiment of the present invention, there is no particular limitation on the vulcanization accelerator. Specifically, a thiazole compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazolyl disulfide), CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) or a guanidine compound such as DPG (diphenylguanidine) can be used. The vulcanization accelerator can be contained in an amount of 0.1 to 5 parts by weight relative to 100 parts by weight of the rubber component.

[0129] According to one embodiment of the present invention, a process oil is used as a softener in the rubber composition. Specific examples thereof include paraffins, cycloparaffins, or aromatic compounds. More specifically, if tensile strength and wear resistance are considered, aromatic process oils can be used, and if hysteresis loss and low-temperature characteristics are considered, cycloparaffinic or paraffinic process oils can be used. The process oil may be included in an amount of 100 parts by weight or less relative to 100 parts by weight of the rubber component. Within this range, deterioration of the tensile strength of the vulcanized rubber and low heat generation (low fuel consumption) can be prevented.

[0130] According to one embodiment of the present invention, the anti-aging agent may be N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 to 6 parts by weight relative to 100 parts by weight of the rubber component.

[0131] According to one embodiment of the present invention, the rubber composition can be obtained by mixing according to the above-mentioned compounding formula using a mixer such as a Banbury mixer, a roller or an internal mixer, and the rubber composition having low heat generation and excellent wear resistance can be obtained by a vulcanization process after the molding process.

[0132] According to one embodiment of the present invention, the rubber composition can be used to manufacture various parts of a tire, such as a tire tread, a bottom tread, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer or a bead coating rubber, or various industrial rubber products, such as anti-vibration rubber, a conveyor belt or a hose. In a specific embodiment, the molded article manufactured using the rubber composition can include a tire or a tire tread.

[0133] Hereinafter, the embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in many different forms and is not limited to the embodiments described in this specification.

[0134] Preparation Example 1

[0135] In a hexane solvent, NdV (neodymium versatate, neodymium 2-ethylhexanoate) and tri-n-octylaluminum (TNOA) were added and stirred at 0°C for 30 minutes for activation, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes for alkylation, and then diethylaluminum chloride (DEAC) was added and stirred at -5°C for 30 minutes to prepare a catalyst composition (NdV:TNOA:DIBAH:DEAC=1:10:15:3 molar ratio).

[0136] Preparation Example 2

[0137] In a hexane solvent, NdV (neodymium versatate, neodymium 2-ethylhexanoate) and tri-n-octylaluminum (TNOA) were added and stirred at 0°C for 30 minutes for activation, triisobutylaluminum (TIBA) was added and stirred at 10°C for 30 minutes for alkylation, and then diethylaluminum chloride (DEAC) was added and stirred at -5°C for 30 minutes to prepare a catalyst composition (NdV:TNOA:TIBA:DEAC = 1:20:30:3 molar ratio).

[0138] Preparation Example 3

[0139] In a hexane solvent, NdV (neodymium versatate, neodymium 2-ethylhexanoate) and triethylaluminum (TEAL) were added and stirred at 0°C for 30 minutes for activation, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes for alkylation, and then diethylaluminum chloride (DEAC) was added and stirred at -5°C for 30 minutes to prepare a catalyst composition (NdV:TEAL:DIBAH:DEAC=1:4:15:3 molar ratio).

[0140] Preparation Example 4

[0141] In a hexane solvent, NdV (neodymium versatate, neodymium 2-ethylhexanoate) and triethylaluminum (TEAL) were added and stirred at 0°C for 30 minutes for activation, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes for alkylation, and then diethylaluminum chloride (DEAC) was added and stirred at -5°C for 30 minutes to prepare a catalyst composition (NdV:TEAL:DIBAH:DEAC=1:2:15:3 molar ratio).

[0142] Preparation Example 5

[0143] In a hexane solvent, NdV (neodymium versatate, neodymium 2-ethylhexanoate) and triethylaluminum (TEAL) were added and stirred at 0°C for 30 minutes for activation, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes for alkylation, and then sesquiethylaluminum chloride (EASC) was added and stirred at -5°C for 30 minutes to prepare a catalyst composition (NdV:TEAL:DIBAH:EASC=1:2:15:1 molar ratio).

[0144] Comparative Preparation Example 1

[0145] In a hexane solvent, NdV (neodymium versatate, neodymium 2-ethylhexanoate) and diisobutylaluminum hydride (DIBAH) were added and stirred at 10°C for 30 minutes for alkylation, and then diethylaluminum chloride (DEAC) was added and stirred at -5°C for 30 minutes to prepare a catalyst composition (NdV:DIBAH:EASC=1:15:3 molar ratio).

[0146] Comparative Preparation Example 2

[0147] In a hexane solvent, NdV (neodymium versatate, neodymium 2-ethylhexanoate) and triisobutylaluminum (TIBA) were added and stirred at 10°C for 30 minutes for alkylation, and then diethylaluminum chloride (DEAC) was added and stirred at -5°C for 30 minutes to prepare a catalyst composition (NdV:DIBAH:EASC=1:30:3 molar ratio).

[0148] Examples and Comparative Examples

[0149] Example 1

[0150] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0151] While the first reactor was maintained at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Preparation Example 1 (0.05 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 90 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 80°C, and polymerization was continued for an additional 15 minutes. The reaction was then terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant. The solvent was removed by steam stripping, and the polymerized product was dried using a hot roller to prepare a conjugated diene polymer.

[0152] Example 2

[0153] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0154] While the first reactor was maintained at 85°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Preparation Example 2 (0.08 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 110 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 85°C, and polymerization was continued for another 15 minutes. Thereafter, a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant were added to terminate the reaction, the solvent was removed by steam stripping, and the polymerized product was dried using a hot roller to prepare a conjugated diene polymer.

[0155] Example 3

[0156] A conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Preparation Example 3 (0.05 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) was used as the catalyst composition in Example 1.

[0157] Example 4

[0158] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0159] While maintaining the temperature of the first reactor at 85°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Preparation Example 3 (0.08 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 110 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 85°C. In this case, 7 kg / hr of 1,3-butadiene was additionally introduced into the second reactor, and polymerization was continued for an additional 15 minutes. Simultaneously, 70% by weight of the total 1,3-butadiene used in the polymer was introduced into the first reactor, and the remaining 30% by weight was introduced into the second reactor. The catalyst composition was based on the total amount of 1,3-butadiene used in the polymer. Thereafter, a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant were added to terminate the reaction, the solvent was removed by steam stripping, and the polymerized product was dried using a hot roll to prepare a conjugated diene-based polymer.

[0160] Example 5

[0161] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0162] While the first reactor was maintained at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Preparation Example 4 (0.05 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 60 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 90°C, and polymerization was continued for another 15 minutes. Thereafter, a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant were added to terminate the reaction, the solvent was removed by steam stripping, and the polymerized product was dried using a hot roller to prepare a conjugated diene polymer.

[0163] Example 6

[0164] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0165] While maintaining the temperature of the first reactor at 75°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Preparation Example 5 (0.08 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 110 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 80°C. In this case, 7 kg / hr of 1,3-butadiene was additionally introduced into the second reactor, and polymerization was continued for an additional 15 minutes. Simultaneously, 70% by weight of the total 1,3-butadiene used in the polymer was introduced into the first reactor, and the remaining 30% by weight was introduced into the second reactor. The catalyst composition was based on the total amount of 1,3-butadiene used in the polymer. Thereafter, a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant were added to terminate the reaction, the solvent was removed by steam stripping, and the polymerized product was dried using a hot roll to prepare a conjugated diene-based polymer.

[0166] Comparative Example 1

[0167] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0168] While the first reactor was maintained at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Comparative Preparation Example 1 (0.05 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 60 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 80°C, and polymerization was continued for another 15 minutes. Thereafter, a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant were added to terminate the reaction, the solvent was removed by steam stripping, and the polymerized product was dried using a hot roller to produce a conjugated diene polymer.

[0169] Comparative Example 2

[0170] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0171] While the first reactor was maintained at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Comparative Preparation Example 2 (0.07 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 60 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 80°C, and polymerization was continued for another 15 minutes. Thereafter, a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant were added to terminate the reaction, the solvent was removed by steam stripping, and the polymerized product was dried using a hot roller to produce a conjugated diene polymer.

[0172] Comparative Example 3

[0173] The conjugated diene-based polymer was prepared using two 80 L stainless steel reactors equipped with a stirrer and a jacket connected in series.

[0174] While the first reactor was maintained at 75°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Preparation Example 5 (0.06 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) were introduced through the upper portion of the first reactor, and polymerization was carried out for 60 minutes. At a point where the polymerization conversion rate reached 80% or higher, the resultant was transferred to a second reactor maintained at 80°C, and polymerization was continued for another 15 minutes. Thereafter, a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant were added to terminate the reaction, the solvent was removed by steam stripping, and the polymerized product was dried using a hot roller to produce a conjugated diene polymer.

[0175] Experimental example

[0176] Experimental Example 1

[0177] For the conjugated diene-based polymers prepared in Examples 1 to 6 and Comparative Examples 1 to 3, Mooney viscosity, molecular weight distribution, cis-1,4 bond content, and viscoelasticity analysis according to frequency change were analyzed as follows, and the results are shown in Table 1 below.

[0178] *Mooney viscosity (ML1+4, @100°C): For each polymer, Mooney viscosity was measured at 100°C using the large rotor of a Monsanto MV2000E at a rotor speed of 2±0.02 rpm. The sample used in this case was allowed to stand at room temperature (23±3°C) for at least 30 minutes, and 27±3 g of the sample was collected and filled into the mold cavity. The Mooney viscosity was measured while operating the platen and applying torque.

[0179] *Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (MWD): Each polymer was dissolved in tetrahydrofuran (THF) at 40°C for 30 minutes, loaded into a gel permeation chromatograph (GPC), and run. In this case, a combination of two PLgel Olexis columns and one PLgelmixed-C column from Polymer Laboratories was used. In addition, all newly replaced columns were mixed bed type columns, and polystyrene was used as the gel permeation chromatography standard material (GPC standard material).

[0180] * Cis-1,4 bond content (wt%): The cis-1,4 bond content of the conjugated diene portion was measured by Fourier transform infrared spectroscopy (FT-IR). Specifically, the FT-IR transmission spectrum of a carbon disulfide solution of a conjugated diene polymer prepared at a concentration of 5 mg / mL was measured using carbon disulfide in the same cell as a blank, and then the FT-IR transmission spectrum at approximately 1130 cm-1 of the measured spectrum was used. -1 The maximum peak (a, baseline), about 967 cm indicating the trans-1,4 bond -1 The minimum peak (b), about 911cm indicating vinyl bond -1 The minimum peak (c) and the peak at about 736 cm indicating the cis-1,4 bond -1 The minimum peak (d) was used to obtain the content.

[0181] *Viscoelasticity analysis by frequency change: In the Tan δ diagram of frequency (Hz) obtained by measuring at 120°C, 0.1% strain, and an angular frequency of 0.01 rad / s to 100 rad / s using a TA Instruments DHR-2 rheometer and 8 mm diameter parallel plates, the following were confirmed: the difference between the maximum and minimum values ​​of the phase angle confirmed in the angular frequency range of 0.01 rad / s to 100 rad / s (Max-Min), the maximum value of the phase angle confirmed in the angular frequency range of 0.01 rad / s to 100 rad / s, the difference between the phase angle at a phase frequency of 1 rad / s and the phase angle at 0.1 rad / s (PA@1 rad / s-PA@0.1 rad / s), and the complex viscosity at the angular frequency. In this case, the sample was prepared by preparing approximately 5 g of polymer, placing it between parallel plates, setting the gap between the parallel plates to 1 mm, and removing the polymer that escaped to the outside before use.

[0182] [Table 1]

[0183]

[0184] From Table 1 above, it can be confirmed that the conjugated diene polymers of Examples 1 to 6 have the properties that meet the requirements of the present invention: the difference between the maximum and minimum values ​​of the phase angle (Max-Min) confirmed in the angular frequency range of 0.01 rad / s to 100 rad / s is 2.3° or more, the maximum value (Max) of the phase angle is 44° or less, the difference between the phase angle at an angular frequency of 1 rad / s and the phase angle at 0.1 rad / s (PA@1rad / s-PA@0.1rad / s) is +1.7° or more, and the complex viscosity at an angular frequency of 0.01 rad / s is 180,000 Pa.s or more.

[0185] Experimental Example 2

[0186] The conjugated diene polymers prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were used to prepare rubber compositions and rubber specimens, and then the Mooney viscosity, tensile properties, viscoelastic properties and wear resistance of the rubber compositions were measured using the following methods. The results are shown in Table 2 below.

[0187] <Formation of Rubber Composition and Rubber Sample>

[0188] Each rubber composition was prepared by mixing 100 parts by weight of each conjugated diene-based polymer of Examples 1 to 6 and Comparative Examples 1 to 3 with 60 parts by weight of carbon black, 15 parts by weight of processing oil (TDAT oil), 3 parts by weight of zinc oxide (ZnO), and 2 parts by weight of stearic acid.

[0189] After that, 1.5 parts by weight of sulfur and 0.9 parts by weight of a vulcanization accelerator (TBBS) were added to each rubber composition and gently mixed at 50° C. and 50 rpm for 2 minutes, and then a 50° C. roller was used to obtain a sheet-like vulcanized mixture. The obtained vulcanized mixture was vulcanized at 160° C. for 20 minutes to prepare a rubber specimen.

[0190] *Mooney viscosity (ML1+4, @100°C): For each rubber composition, the Mooney viscosity was measured at 100°C using a Monsanto MV2000E large rotor at a rotor speed of 2±0.02 rpm. The sample used in this case was left at room temperature (23±3°C) for at least 30 minutes, 27±3 g of which was collected and filled into a mold cavity. The press plate was operated to apply torque while the Mooney viscosity was measured. In addition, the difference (ΔMV) between the measured Mooney viscosity of the rubber composition and the Mooney viscosity of the conjugated diene polymer measured in Experimental Example 1 was calculated.

[0191] Furthermore, the measured value of Comparative Example 1 was used as a reference value, and the difference in Mooney viscosity between each Example and Comparative Example was indexed using the following equation 1, and the processability was confirmed by this value, with the larger the value, the better.

[0192] [Equation 1]

[0193] Processing performance = {[(reference value - measured value) / reference value] × 100} + 100

[0194] *Tensile properties: After each of the rubber compositions prepared above was vulcanized at 150° C. for 90 minutes, the modulus of the vulcanized product at 300% elongation (M-300%, kg·f / cm 2 ). The measured value of Comparative Example 1 was used as a reference value, and the 300% modulus of each Example and Comparative Example was indexed using the following Equation 2. The higher the value, the better.

[0195] [Equation 2]

[0196] M-300% index = (measured value / reference value) × 100

[0197] *Viscoelastic properties: Viscoelastic coefficient (Tan δ) at -60°C to 60°C was measured using a DMTS 500N from Gabo, Germany, at a frequency of 10 Hz, a 3% pre-strain, and a 3% dynamic strain. In this case, the Tan δ value at 60°C represents rolling resistance characteristics (fuel efficiency). The measured value of Comparative Example 1 was used as a reference value, and the viscoelastic properties of each Example and Comparative Example were indexed using Equation 3 below.

[0198] [Equation 3]

[0199] Tanδ@60℃ index = {[(reference value - measured value) / reference value] × 100} + 100

[0200] *Abrasion resistance: For each rubber specimen formed above, a DIN abrasion test was performed according to ASTM D5963 and expressed as a DIN weight loss index (loss volume index: ARIA (Abrasion Resistance Index, Method A)). The measured value of Comparative Example 1 was used as a reference value, and the abrasion resistance of each Example and Comparative Example was indexed using the following equation 4.

[0201] [Equation 4]

[0202] Wear index={[(reference value-measured value) / reference value]×100}+100.

[0203] [Table 2]

[0204]

[0205] As shown in Table 2 above, Examples 1 to 6 exhibited improved wear resistance and significantly increased processability while maintaining tensile properties and viscoelasticity at the same levels as Comparative Examples 1 to 3.

[0206] From this result, it can be confirmed that the conjugated diene polymer of the present invention exhibits improved processing performance by introducing branches into the linear conjugated diene polymer, while maintaining the properties of the conjugated diene polymer other than the processing performance at the level of the high linear conjugated diene polymer and maintaining the mixing performance in the rubber composition at a high level.

Claims

1. A conjugated diene polymer: Containing conjugated diene monomer units, It has a cis bond content of 95.0% by weight or more, When dynamic viscoelasticity analysis is performed based on frequency variation, the difference (Max-Min) between the maximum and minimum phase angles confirmed within the range of angular frequency from 0.01 rad / s to 100 rad / s is 2.3° or more.

2. The conjugated diene polymer according to claim 1, wherein When dynamic viscoelasticity analysis was performed based on frequency variation, the maximum value (Max) of the phase angle confirmed within the angular frequency range of 0.01 rad / s to 100 rad / s was 44° or less.

3. The conjugated diene polymer according to claim 1, wherein If dynamic viscoelasticity analysis is performed based on frequency variation, the difference between the phase angle at an angular frequency of 1 rad / s and the phase angle at an angular frequency of 0.1 rad / s (PA@1rad / s - PA@0.1rad / s) is +1.7° or more.

4. The conjugated diene polymer according to claim 1, wherein When dynamic viscoelasticity analysis is performed based on frequency changes, the complex viscosity at an angular frequency of 0.01 rad / s is 180,000 Pa·s or more. The conjugated diene polymer according to claim 1 , wherein The conjugated diene-based polymer includes a branched chain. The conjugated diene polymer according to claim 1 , wherein The number average molecular weight is 200,000 g / mol to 400,000 g / mol.

7. The conjugated diene polymer according to claim 1, wherein The weight average molecular weight is 500,000 g / mol to 800,000 g / mol.

8. The conjugated diene polymer according to claim 1, wherein The molecular weight distribution is 2.0 to 3.

0.

9. The conjugated diene polymer according to claim 1, wherein Mooney viscosity (ML1+4@100℃) is 40 to 65. 10 . A rubber composition comprising the conjugated diene-based polymer according to claim 1 .

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