Conjugated diene-based polymer and rubber composition

Abstract

The present invention relates to: a conjugated diene-based polymer which is a linear conjugated diene-based polymer having a branch introduced thereto to retain the physical properties of the conjugated diene-based polymer, except for processability, comparable with those of a conjugated diene-based polymer having high linearity and thus superbly maintains the compounding properties in a rubber composition and also exhibits improved processability; and a rubber composition comprising the conjugated diene-based polymer.

Description

Conjugated diene polymer and rubber composition

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0149216, filed November 1, 2023, the entire contents of which are incorporated herein by reference.

[0003] [Technical Field]

[0004] The present invention relates to a conjugated diene polymer and a rubber composition comprising the same.

[0005]

[0006] With growing interest in energy conservation and environmental issues, there is a growing demand for improved fuel efficiency in automobiles. One approach to achieving this goal has been proposed: increasing the cis bond content and linearity of polybutadiene in tire-forming rubber compositions while narrowing the molecular weight distribution.

[0007] Polybutadiene can be produced using a Ziegler-Natta catalyst, and the Ziegler-Natta catalyst is produced by activating an organic acid metal compound with an alkyl aluminum and a halogenated alkyl aluminum compound, and reacting the produced catalyst with a 1,3-butadiene monomer to produce polybutadiene.

[0008] Here, the organic acid metal compounds include titanium-based, nickel-based, cobalt-based, and lanthanum-based compounds, and lanthanum-based 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.

[0009] Representative examples of the above lanthanide rare earth element compounds include neodymium compounds, and specific examples include NdV (neodymium versatate). These are activated through an alkylation reaction using an alkyl aluminum compound, followed by a halogenation reaction using a halogenated alkyl aluminum compound. In order to stabilize the catalyst, a 1,3-butadiene monomer is added during the alkylation reaction to perform preforming.

[0010] However, polybutadiene manufactured from a catalyst manufactured using the above-mentioned lanthanide rare earth element compounds, especially neodymium compounds, has improved physical properties, but has the problem of poor processability due to high linearity.

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] (Patent Document 1) US 9056303 B2

[0014]

[0015] The problem to be solved in the present invention is to improve processability while maintaining the properties of a conjugated diene polymer at the level of highly linear polybutadiene.

[0016] That is, the present invention aims to provide a conjugated diene polymer having improved processability while maintaining the physical properties of the conjugated diene polymer, excluding processability, at the level of a highly linear conjugated diene polymer, thereby maintaining the mixing properties in a rubber composition at a high level, in order to solve the problems mentioned in the background technology of the above invention.

[0017] In addition, the present invention aims to provide a rubber composition comprising the above conjugated diene polymer.

[0018]

[0019] To solve the above problem, the present invention provides a conjugated diene polymer and a rubber composition.

[0020] (1) The present invention provides a conjugated diene polymer comprising a conjugated diene monomer unit, having a 1,4-cis bond content of 95.0 wt% or more, and having a difference (Max-Min) between the maximum and minimum values ​​of a phase angle confirmed in an angular frequency range of 0.01 rad / s to 100 rad / s of 2.3° or more when a dynamic viscoelasticity analysis is performed according to a change in frequency.

[0021] (2) The present invention provides a conjugated diene polymer having a maximum value (Max) of a phase angle of 44° or less confirmed in the angular frequency range of 0.01 rad / s to 100 rad / s when dynamic viscoelasticity analysis is performed according to frequency change in the above (1).

[0022] (3) The present invention provides a conjugated diene polymer in which, when a dynamic viscoelasticity analysis is performed according to a change in frequency in the above (1) or (2), the difference between the phase angle at an angular frequency of 1 rad / s and the phase angle at 0.1 rad / s (PA@1 rad / s - PA@0.1 rad / s) is +1.7° or more.

[0023] (4) The present invention provides a conjugated diene polymer having a complex viscosity of 180,000 Pa.s or more at an angular frequency of 0.01 rad / s when dynamic viscoelasticity analysis is performed according to frequency change in any one of the above (1) to (3).

[0024] (5) The present invention provides a conjugated diene polymer according to any one of the above (1) to (4), wherein the conjugated diene polymer includes a branched chain.

[0025] (6) The present invention provides a conjugated diene polymer having a number average molecular weight of 200,000 g / mol or more and 400,000 g / mol or less in any one of the above (1) to (5).

[0026] (7) The present invention provides a conjugated diene polymer having a weight average molecular weight of 500,000 g / mol or more and 800,000 g / mol or less in any one of the above (1) to (6).

[0027] (8) The present invention provides a conjugated diene polymer having a molecular weight distribution of 2.0 or more and 3.0 or less in any one of the above (1) to (7).

[0028] (9) The present invention provides a conjugated diene polymer having a Mooney viscosity (ML1+4 @100°C) of 40 or more and 65 or less in any one of the above (1) to (8).

[0029] (10) The present invention provides a rubber composition comprising a conjugated diene polymer according to any one of (1) to (9).

[0030]

[0031] The conjugated diene polymer of the present invention exhibits improved processability while maintaining the physical properties of the conjugated diene polymer, except for processability, at the level of a highly linear conjugated diene polymer by introducing a branch into the linear conjugated diene polymer, thereby maintaining the mixing properties in the rubber composition at a high level.

[0032]

[0033] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0034] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0035] measurement method

[0036] In this specification, the '1,4-cis bond content (wt%)' is the cis-1,4 bond content of the conjugated diene moiety measured by Fourier transform infrared spectroscopy (FT-IR). After measuring the FT-IR transmittance spectrum of the carbon disulfide solution of the conjugated diene polymer prepared at a concentration of 5 mg / mL using carbon disulfide in the same cell as a blank, the 1130 cm of the measured spectrum -1 The maximum peak value near (a, baseline) is 967 cm, indicating a trans-1,4 bond. -1 The minimum peak value near (b) is 911 cm, indicating vinyl bonding. -1 The minimum peak value (c) near 736 cm, indicating a cis-1,4 bond. -1 Each content was obtained using the minimum peak value (d) in the vicinity.

[0037] In this specification, 'Mooney viscosity (ML1+4, @100℃)' was measured using a Monsanto MV2000E Large Rotor under the conditions of a rotor speed of 2±0.02 rpm at 100℃, after leaving the polymer at room temperature (23±3℃) for more than 30 minutes, collecting 27±3 g and filling it inside the die cavity, and applying torque by operating the platen.

[0038] 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. At this time, two PLgel Olexis columns and one PLgel mixed-C column, trade names of Polymer Laboratories, were used in combination. 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).

[0039] In this specification, viscoelasticity analysis according to frequency change was measured using a DHR-2 rheometer from TA Instruments and a parallel plate with a diameter of 8 mm under conditions of 120°C, 0.1% strain, and an angular frequency ranging from 0.01 rad / s to 100 rad / s.

[0040]

[0041] conjugated diene polymer

[0042] The present invention provides a conjugated diene polymer having improved processability characteristics while maintaining excellent physical properties in terms of tensile properties, viscoelastic properties, and wear resistance of a highly linear conjugated diene polymer.

[0043] According to one embodiment of the present invention, the conjugated diene polymer may be a linear conjugated diene polymer with a branch introduced thereto. In this case, the branch is formed without adding a monomer containing the branch, a modifier, or the like, and in the present invention, the branch is defined based on the results of a dynamic viscoelasticity analysis according to a change in frequency, which will be described later.

[0044] According to one embodiment of the present invention, the conjugated diene polymer includes a conjugated diene monomer unit, has a 1,4-cis bond content of 95.0 wt% or more, and when a dynamic viscoelasticity analysis is performed according to a change in frequency, the 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 may be 2.3° or more.

[0045]

[0046] Polybutadiene is generally manufactured by polymerizing 1,3-butadiene monomer using a Ziegler-Natta catalyst, which is manufactured by activating an organic acid metal compound with an alkyl aluminum and a halogenated alkyl aluminum compound. Here, a lanthanide series rare earth element compound, such as a neodymium compound, is widely used as one of the organic acid metal compounds, and is activated through an alkylation reaction using an alkyl aluminum compound, followed by a halogenation reaction using a halogenated alkyl aluminum compound. In order to stabilize the catalyst, a 1,3-butadiene monomer is sometimes added during the alkylation reaction to perform preforming. However, polybutadiene manufactured from a catalyst manufactured using the above-mentioned lanthanide rare earth element compounds, especially neodymium compounds, has high compounding properties such as tensile properties, viscoelastic properties, and wear resistance, but has a problem in that the compounding processability is considerably poor due to high linearity.

[0047] According to the present invention, the conjugated diene polymer is manufactured using a lanthanide rare earth element compound as a main catalyst, and by controlling the catalyst composition and polymerization conditions, a branched chain is introduced into the structure of the polymer chain formed by polymerization, thereby maintaining excellent compounding properties such as tensile properties, viscoelastic properties, and wear resistance originally developed due to high linearity, while at the same time improving compounding processability. According to one embodiment of the present invention, the conjugated diene intermediate may include a conjugated diene monomer unit, and may have a 1,4-cis bond content of 95.0 wt% or more, and at the same time, when a dynamic viscoelasticity analysis is performed according to a change in frequency, the difference (Max-Min) between the maximum value and the minimum value of the phase angle confirmed in the angular frequency (angular frequency) range of 0.01 rad / s to 100 rad / s may be 2.3° or more.

[0048] Specifically, the conjugated diene polymer has a 1,4-cis bond content of 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, 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% It may be 97.5 wt% or more, or 100.0 wt% or less, 99.5 wt% or less, or 99.0 wt% or less.

[0049] In addition, when the above conjugated diene polymer is subjected to a dynamic viscoelasticity analysis according to a change in frequency, the 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 may be 2.3° or more, or 2.35° or more, or 2.40° or more, and also 3.5° or less, 3.30° or less, or 3.10° or less.

[0050]

[0051] In addition, according to one embodiment of the present invention, when the conjugated diene polymer is subjected to a dynamic viscoelasticity analysis according to a change in frequency, the maximum value (Max) of the phase angle confirmed in the 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 further 38° or more, 38.5° or more, or 39° or more.

[0052]

[0053] In addition, when the conjugated diene polymer is subjected to a dynamic viscoelasticity analysis according to a change in frequency, the difference between the phase angle at an angular frequency of 1 rad / s and the phase angle at 0.1 rad / s (PA@1 rad / s - PA@0.1 rad / s) may be +1.7° or more. Here, PA@1 rad / s and PA@0.1 rad / s mean PA at 1 rad / s and PA at 0.1 rad / s, respectively. Specifically, the difference in the phase angle (PA@1 rad / s - PA@0.1 rad / s) may be +1.71° or more or +1.73° or more, and also +3.50° or less, +3.00° or less, or +2.90° or less.

[0054] According to one embodiment of the present invention, when dynamic viscoelasticity analysis is performed on the conjugated diene polymer according to frequency change, the complex viscosity at an angular frequency of 0.01 rad / s may be 180,000 Pa.s or more. Specifically, the complex viscosity may be 180,000 Pa.s or more and 500,000 Pa.s or less, or 180,000 Pa.s or more and 300,000 Pa.s or less.

[0055] Depending on the branch chain and the length of the branch chain in the conjugated diene polymer, the difference between the maximum and minimum values ​​of the phase angle (Max-Min), the difference between the phase angle (PA@1 rad / s - PA@0.1 rad / s), and the complex viscosity vary, and as the branch chain and the length of the branch chain increase, the difference between the maximum and minimum values ​​of the phase angle (Max-Min) and the difference between the phase angle (PA@1 rad / s - PA@0.1 rad / s) increase, and the complex viscosity at a low angular frequency (0.01 rad / s) tends to increase and the complex viscosity at a high angular frequency (1.0 rad / s) tends to decrease.

[0056] In one embodiment of the present invention, the copolymer polymer can improve cold flow and processability by satisfying the difference between the maximum and minimum values ​​of the phase angle (Max-Min), the difference in phase angle (PA@1 rad / s - PA@0.1 rad / 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@1 rad / s - PA@0.1 rad / s), and the complex viscosity may mean that the polymer contains a branch chain of an appropriate length in an appropriate ratio.

[0057] According to one embodiment of the present invention, a conjugated diene polymer is provided, wherein the conjugated diene polymer includes a branched chain.

[0058]

[0059] According to one embodiment of the present invention, the conjugated diene polymer may include a conjugated diene monomer unit. The conjugated diene monomer unit refers to a repeating unit formed by polymerization of a conjugated diene monomer.

[0060] 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 a 1,3-butadiene monomer unit, 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 decrease in the cis-1,4 bond content in the conjugated diene polymer may be prevented. The above 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, and other conjugated diene monomers copolymerizable with the above 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.

[0061] According to one embodiment of the present invention, the conjugated diene polymer may be a conjugated diene polymer catalyzed by a catalyst composition comprising a lanthanide series rare earth element compound. That is, the conjugated diene polymer may be a conjugated diene polymer including an organometallic moiety activated by a catalyst composition comprising a neodymium compound.

[0062]

[0063] 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 tensile properties are excellent, and the processability is excellent, so that the workability of the rubber composition is improved, making it easy to knead, and thus the mechanical properties and property balance of the rubber composition are excellent.

[0064] 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 processability is excellent, so that the workability of the rubber composition is improved, making it easy to knead, and thus the mechanical properties and property balance of the rubber composition are excellent.

[0065] According to one embodiment of the present invention, the conjugated diene polymer may have a molecular weight distribution (Mw / Mn) of 2.0 or more and 3.0 or less. The molecular weight distribution can be calculated from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). Here, the number average molecular weight (Mn) is a common average of individual polymer molecular weights calculated by measuring the molecular weights of n polymer chains, calculating the sum of these molecular weights, and dividing by n, and the weight average molecular weight (Mw) represents the molecular weight distribution of the polymer composition. All molecular weight averages can be expressed in grams per mole (g / mol). In addition, the weight average molecular weight and the number average molecular weight may each mean a polystyrene-converted molecular weight analyzed by gel permeation chromatography (GPC).

[0066] According to one embodiment of the present invention, when the conjugated diene polymer simultaneously satisfies the conditions of weight average molecular weight (Mw) and number average molecular weight along with the molecular weight distribution, when applied to a rubber composition, the rubber composition has excellent tensile properties, viscoelasticity, and processability, and has an excellent balance of physical properties therebetween.

[0067]

[0068] According to one embodiment of the present invention, the conjugated diene polymer may have a Mooney viscosity (ML1+4, @100°C) of 40 or more and 65 or less. Here, @100°C means at 100°C.

[0069]

[0070] Method for producing conjugated diene polymers

[0071] The present invention provides a method for producing a conjugated diene polymer. The method for producing a conjugated diene polymer may be a method for producing the conjugated diene polymer described above.

[0072] According to one embodiment of the present invention, the method for producing a conjugated diene polymer may include a step (S100) of producing an active polymer by polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition.

[0073] 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 reactant of the lanthanide rare earth element compound, the alkylating agent, and the halide.

[0074] According to one embodiment of the present invention, the lanthanide series rare earth element compound may 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-ethyl hexanoate, neodymium neodecanoate, etc.); Organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl phosphate, etc.); Organophosphonates (e.g., neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium(1-methylheptyl) phosphonate, neodymium(2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate, or neodymium octadecyl phosphonate, etc.); Organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl) phosphinate, or neodymium (2-ethylhexyl) phosphinate); carbamates (e.g., neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate, or neodymium dibenzyl carbamate); dithiocarbamates (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate, or neodymium dibutyldithiocarbamate); Xanthogenates (e.g., neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl xanthogenate, or neodymium benzyl xanthogenate);β-diketonates (e.g., neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate, or neodymium benzoylacetonate); alkoxides or allyloxides (e.g., neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide, or neodymium nonyl phenoxide); halides or pseudohalides (e.g., neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); oxyhalides (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide); Or organic neodymium compounds containing one or more rare earth element-carbon bonds (e.g., Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, or Ln(allyl)2Cl, etc., where Ln is a rare earth metal element and R is a hydrocarbyl group), and the like, and may include any one or a mixture of two or more thereof.;

[0075] According to one embodiment of the present invention, the lanthanide series rare earth element compound may be a neodymium compound represented by the following chemical formula 1.

[0076] [Chemical Formula 1]

[0077]

[0078] In the above chemical formula 1, R 1 Inland R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 Inland R 3 All of these may not be hydrogen. As a specific example, in the above chemical formula 1, R 1 is an alkyl group having 4 to 12 carbon atoms, and R 2 and R3 Each independently represents hydrogen or an alkyl group having 2 to 8 carbon atoms, and R 2 and R 3 All of these may not be hydrogen. For a more specific example, in the above chemical formula 1, R 1 is an alkyl group having 6 to 8 carbon atoms, and R 2 and R 3 Each independently represents hydrogen or an alkyl group having 2 to 6 carbon atoms, and R 2 and R 3 All of these may not be hydrogen.

[0079] According to one embodiment of the present invention, the lanthanide rare earth element compound is Nd(2-ethyl hexanoate)3 (or neodymium versatate), Nd(2,2-dimethyl decanoate)3, Nd(2,2-diethyl decanoate)3, Nd(2,2-dipropyl decanoate)3, Nd(2,2-dibutyl decanoate)3, Nd(2,2-dihexyl decanoate)3, Nd(2,2-dioctyl decanoate)3, Nd(2-ethyl-2-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd(2-hexyl-2-octyl decanoate)3, Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl It may be at least one selected from the group consisting of Nd(2,2-dihexyl nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3, and Nd(2-ethyl-2-hexyl nonanoate)3.

[0080] According to one embodiment of the present invention, the neodymium compound includes a carboxylate ligand having an alkyl group of various lengths having 2 or more carbon atoms as a substituent at the α-position, thereby inducing a steric change around the neodymium central metal, thereby preventing aggregation between compounds, and thus has the effect of suppressing oligomerization during polymerization of a conjugated diene polymer using the catalyst composition. In addition, such a neodymium compound has high solubility in a solvent, and has the effect of reducing the proportion of neodymium located in the central portion, which is difficult to convert to a catalytically active species, thereby increasing the conversion rate to a catalytically active species.

[0081] According to one embodiment of the present invention, the solubility of the neodymium compound may be about 60 parts by weight or more per 100 parts by weight of a non-polar solvent at room temperature (25°C). The solubility of the neodymium compound refers to the degree to which it dissolves clearly without cloudiness, and by exhibiting such high solubility, it can exhibit excellent catalytic activity.

[0082] According to one embodiment of the present invention, the alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and may function as a cocatalyst. The alkylating agent may be an organometallic compound that is soluble in a polymerization solvent and contains a metal-carbon bond, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound.

[0083] According to one embodiment of the present invention, the alkylating agent may be an organoaluminum compound, and specific examples thereof include alkyl aluminum such as tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; Diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride (DIBAH), di-n-octyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenylisopropyl aluminum hydride, phenyl-n-butyl aluminum hydride, phenylisobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolylisopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolylisobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzylethyl aluminum hydride, benzyl-n-propyl aluminum Dihydrocarbylaluminum hydrides such as hydride, benzylisopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzylisobutyl aluminum hydride or benzyl-n-octyl aluminum hydride; hydrocarbylaluminum dihydrides such as ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride or n-octyl aluminum dihydride;

[0084] According to one embodiment of the present invention, the alkylating agent may be an alkyl aluminum compound represented by the following chemical formula 2.

[0085] [Chemical Formula 2]

[0086] AlR 4 R 5 R 6

[0087] In the above chemical formula 2, R 4 Inland R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 4 Inland R 6 Not all of these are hydrogen, and tri-n-hexyl aluminum and tri-n-octyl aluminum may not be included. As a specific example, in the above chemical formula 2, R 4 Inland R 6 are each independently hydrogen or an alkyl group having 3 to 8 carbon atoms, and R 4 Inland R 6 Not all of these are hydrogen, and tri-n-hexyl aluminum and tri-n-octyl aluminum may not be included. As a more specific example, in the above chemical formula 2, R 4 Inland R 6 Each independently represents hydrogen or an alkyl group having 3 to 5 carbon atoms, and R 4 Inland R 6 All of these may not be hydrogen.

[0088] According to one embodiment of the present invention, the alkylating agent may include two or more alkyl aluminum compounds. As a specific example, the alkylating agent may include two or more selected from the group consisting of dialkyl aluminum hydride and trialkyl aluminum. As a more specific example, the alkylating agent may include one or more dialkyl aluminum hydride and one or more trialkyl aluminum, and as a still more specific example, the alkylating agent may include diisobutyl aluminum hydride and triisobutyl aluminum or diisobutyl aluminum hydride and triethyl aluminum.

[0089] According to one embodiment of the present invention, the catalyst composition may be carried out by introducing an alkylating agent in 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 per mol of the lanthanide series rare earth element compound, and may also include the alkylating agent in 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.

[0090] According to one embodiment of the present invention, the halide may be a halogen compound, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometallic halide.

[0091] According to one embodiment of the present invention, the halogen group may be fluorine, chlorine, bromine or iodine.

[0092] According to one embodiment of the present invention, the halogen compound may be iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, or iodine trifluoride.

[0093] According to one embodiment of the present invention, the hydrogen halide may be hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide.

[0094] According to one embodiment of the present invention, the organic halide is t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called 'iodoform'), tetraiodomethane, 1-iodopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called 'neopentyl iodide'), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide or methyl iodoformate.

[0095] According to one embodiment of the present invention, the non-metal halide may 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.

[0096] According to one embodiment of the present invention, the metal halide may 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 tetraiodide, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

[0097] According to one embodiment of the present invention, the organometallic halide may be an alkyl aluminum halide or an alkyl aluminum sesquihalide.As a specific example, the organometallic halide is dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, methyl aluminum difluoride, ethyl aluminum difluoride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride (EASC), isobutyl aluminum sesquichloride, methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride, trimethyl tin chloride, trimethyl tin bromide, triethyl tin chloride, triethyl tin bromide, di-t-butyl tin dichloride, Di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide, methyl magnesium iodide, dimethyl aluminum iodide, diethyl aluminum iodide, di-n-butyl aluminum iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, methyl aluminum sesquiiodide, ethyl aluminum sesquiiodide, isobutyl aluminum sesquiiodide, ethyl magnesium iodide, n-butyl magnesium iodide, isobutyl magnesium iodide, phenyl magnesium iodide, benzyl magnesium iodide, trimethyl tin It may be iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin diiodide or di-t-butyltin diiodide.

[0098] According to one embodiment of the present invention, the halide may be at least one selected from the group consisting of an alkyl aluminum halide represented by the following chemical formula 3 and an alkyl aluminum sesquihalide represented by the following chemical formula 4, from the viewpoint of improving catalytic activity and thus reactivity.

[0099] [Chemical Formula 3]

[0100] AlR 7 R 8 R 9

[0101] In the above chemical formula 3, R 7 Inland R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R 7 Inland R 9 Not all of them may be halogen groups. As a specific example, in the above chemical formula 3, R 7 Inland R 9 are each independently a halogen group or an alkyl group having 1 to 6 carbon atoms, and R 7 Inland R 9 Not all of them may be halogen groups. As a more specific example, in the above chemical formula 3, R 7 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms, and R 9 may be a halogen group.

[0102] [Chemical Formula 4]

[0103]

[0104] In the above chemical formula 4, R 10 Inland R 12 Each of may independently be an alkyl group having 1 to 12 carbon atoms, and X1 to X3 may each independently be a halogen group. As a specific example, in the chemical formula 4, R 10 Inland R 12 Each of may independently be an alkyl group having 1 to 6 carbon atoms. As a more specific example, in the chemical formula 4, R10 Inland R 12 Each may independently be an alkyl group having 1 to 4 carbon atoms.

[0105] According to one embodiment of the present invention, the halide may be at least one selected from the group consisting of dialkyl aluminum halides and alkyl aluminum sesquihalides, and the types of the dialkyl aluminum halides and alkyl aluminum sesquihalides are as described above. As a specific example, the dialkyl aluminum halide may be diethyl aluminum chloride, and the alkyl aluminum sesquihalide may be ethyl aluminum sesquichloride.

[0106] According to one embodiment of the present invention, the catalyst composition may include the halide in 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 per mol of the lanthanide series rare earth element compound. In addition, the catalyst composition may include the halide in 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 per mol of the lanthanide series rare earth element compound.

[0107] 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 is not reactive with the components of the catalyst composition. As a specific example, the organic solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 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 or methylcyclohexane; a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether, petroleum spirits or kerosene; or an aromatic hydrocarbon solvent, such as benzene, toluene, ethylbenzene or xylene. As a more specific example, the organic solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, preferably n-hexane, cyclohexane or a mixture thereof.

[0108] Meanwhile, according to one embodiment of the present invention, the catalyst composition may be manufactured by stirring a lanthanide series rare earth element compound and a first alkylating agent in an organic solvent to pre-activate, adding a second alkylating agent thereto and stirring to alkylate, and then adding a halide to halogenate. Here, the first alkylating agent may be at least one selected from the aforementioned trialkyl aluminum, and the second alkylating agent may be at least one selected from the aforementioned dialkyl aluminum hydride. The pre-activation may be performed by stirring at a temperature of 0°C to 40°C, the alkylation may be performed by stirring at a temperature of -10°C to 30°C, and the halogenation may be performed by stirring at a temperature of -20°C to 20°C.

[0109] When a catalyst composition is prepared under the above conditions, the catalyst activity can be maximized, and when polymerizing a conjugated diene monomer, the polymerization of the monomer is rapidly promoted, thereby increasing the reaction between polymer chains, which can be advantageous in ultimately preparing a conjugated diene monomer with an appropriately introduced branch chain.

[0110] According to one embodiment of the present invention, the conjugated diene monomer that can be introduced in the step (S100) may be at least one selected from the group consisting of 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.

[0111] According to one embodiment of the present invention, the hydrocarbon solvent of the step (S100) may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0112] According to one embodiment of the present invention, the catalyst composition may be used in an amount such 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, with respect to a total of 100 g of the conjugated diene monomer, and may also be used in an amount such 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.

[0113] According to one embodiment of the present invention, the polymerization in step (S100) may be performed as a continuous polymerization in a polymerization reactor comprising at least two reactors, or may be performed in a batch reactor. In addition, the polymerization may be a temperature-elevated polymerization, an isothermal polymerization, or a constant-temperature polymerization (adiabatic polymerization).

[0114] According to one embodiment of the present invention, the isothermal polymerization means polymerizing with the heat of reaction itself without arbitrarily applying heat after introducing the catalyst composition, the temperature-increasing polymerization means increasing the temperature by arbitrarily applying heat after introducing the catalyst composition, and the isothermal polymerization means increasing the temperature by applying heat or removing heat after introducing the catalyst composition to keep the temperature of the reactants constant.

[0115] According to one embodiment of the present invention, the polymerization in the step (S100) may be carried out using coordination anionic polymerization, and the polymerization environment may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and a specific example may be solution polymerization.

[0116] According to one embodiment of the present invention, the polymerization in the step (S100) can be carried out at a temperature of -20°C or higher, -10°C or higher, 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher, and can also be carried out at a temperature of 200°C or lower, 150°C or lower, 120°C or lower, or 90°C or lower, and within this range, the polymerization reaction can be smoothly controlled while securing the cis-1,4 bond content of the produced conjugated diene polymer.

[0117] According to one embodiment of the present invention, the polymerization in step (S100) may be performed for 15 minutes or more, 20 minutes or more, 30 minutes or more, 40 minutes or more, 50 minutes or more, or 1 hour or more, and may also be performed for 3 hours or less, 2 hours and 30 minutes or less, or 2 hours or less.

[0118] As another example, according to one embodiment of the present invention, the polymerization in the step (S100) may be performed as a continuous polymerization using a continuous reactor in which two or more, or two or more but not more than ten, or two or more but not more than five, or two or more but not more than four reactors are connected in series, and in this case, it may be more advantageous for producing a conjugated diene polymer having the above-described characteristics and having a branched chain introduced.

[0119] In addition, according to one embodiment of the present invention, the polymerization in the step (S100) may be performed for 60 minutes or more, 70 minutes or more, 80 minutes or more, 90 minutes or more, or 180 minutes or less, 150 minutes or less, or 120 minutes or less, in which case it may be more advantageous for producing a conjugated diene polymer having the above-described characteristics with branched chains introduced.

[0120] In addition, according to one embodiment of the present invention, the polymerization of the step (S100) may be performed by dividing the conjugated diene monomer into two or more parts, and in the case of dividing the conjugated diene monomer into two or more parts, the amount of the conjugated diene monomer introduced after the second time may be 20 parts by weight to 40 parts by weight, or 25 parts by weight to 35 parts by weight, based on 100 parts by weight of the total conjugated diene monomer introduced during the polymerization. In addition, in the case of dividing the conjugated diene monomer into three or more parts, the respective amounts of the conjugated diene monomer introduced into the second, third, and n-th times may be appropriately distributed and introduced based on the amount of the conjugated diene monomer introduced after the second time.

[0121] In addition, in the case of dividing and introducing the conjugated diene monomer, the conjugated diene monomer introduced in dividing portions after the initial stage may be introduced at a time when the polymerization conversion rate of the initially introduced conjugated diene monomer is 50% or more, 60% or more, or 70% or more, or 90% or less, 85% or less, or 80% or less.

[0122] According to one embodiment of the present invention, the conjugated diene polymer formed by the polymerization in the step (S100) may be an active polymer including a site activated by a catalyst composition.

[0123] According to one embodiment of the present invention, the method may include a step (S200) of reacting the active polymer with a modifier. The modifier may be a known modifier that can be used when producing a conjugated diene polymer using a catalyst composition containing a lanthanide series rare earth element compound.

[0124] According to one embodiment of the present invention, the method for producing the conjugated diene polymer may further include a step of terminating the polymerization by further using an additive, such as a reaction terminator for completing the polymerization reaction, such as polyoxyethylene glycol phosphate, or an antioxidant, such as 2,6-di-t-butylparacresol, after producing the active polymer. In addition, an additive that facilitates solution polymerization, such as a chelating agent, a dispersing agent, a pH regulator, a deoxidizer, or an oxygen scavenger, may be optionally further used together with the reaction terminator.

[0125]

[0126] The method for producing the conjugated diene polymer according to one embodiment of the present invention may be performed by appropriately selecting and combining conditions within the above-described method so that a conjugated diene polymer satisfying the above-described parameters can be produced, and specifically, the method may be performed by appropriately selecting and controlling the catalyst composition production conditions, such as the pre-activation step, polymerization time, monomer splitting, reactor temperature, and catalyst input amount, so that a conjugated diene polymer satisfying the above-described parameters can be produced.

[0127]

[0128] rubber composition

[0129] The present invention provides a rubber composition.

[0130] According to one embodiment of the present invention, the rubber composition may include the conjugated diene polymer. As a specific example, the rubber composition may include the conjugated diene polymer in an amount of 0.1 wt% or more, 10 wt% or more, or 20 wt% or more, and further, may include the conjugated diene polymer in an amount of 100 wt% or less, 95 wt% or less, or 90 wt% or less, and within this range, the wear resistance and crack resistance of a molded article, for example, a tire, manufactured using the rubber composition can be sufficiently secured.

[0131] According to one embodiment of the present invention, the rubber composition may further include other rubber components as needed in addition to the conjugated diene polymer. In this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, the rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the conjugated diene copolymer.

[0132] According to one embodiment of the present invention, the rubber component may be natural rubber or synthetic rubber, and for example, the rubber component may be natural rubber (NR) including cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or purified natural rubbers; It may be a synthetic rubber such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, 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, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and any one or a mixture of two or more of these may be used.

[0133] According to one embodiment of the present invention, the rubber composition may have a difference of 30 or less 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. As a specific example, the rubber composition may have a difference 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 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. 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, when the difference between the Mooney viscosity (ML1+4 @100℃) of the conjugated diene polymer and the Mooney viscosity (ML1+4 @100℃) of the rubber composition is adjusted within the above range, the processability can be particularly improved.

[0134] 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. As a specific example, 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 above rubber composition may vary depending on other components included in the rubber composition in addition to the conjugated diene polymer, but when adjusted within the above range, processability may be particularly improved.

[0135] According to one embodiment of the present invention, the rubber composition may contain a filler in an amount of 20 parts by weight or more and 90 parts by weight or less, based on 100 parts by weight of the conjugated diene polymer. The filler may be a silica-based filler, a carbon black-based filler, or a combination thereof. As a specific example, the filler may be a carbon black-based filler.

[0136] According to one embodiment of the present invention, the carbon black filler has a nitrogen adsorption surface area (N2SA, measured in accordance with JIS K 6217-2:2001) of 20 m 2 / g to 250 m 2 / g, and within this range, the rubber composition can have excellent processability while sufficiently securing reinforcing performance by the filler. In addition, the carbon black-based filler can have a dibutyl phthalate absorption (DBP) of 80 cc / 100g to 200 cc / 100g, and within this range, the rubber composition can have excellent processability while sufficiently securing reinforcing performance by the filler.

[0137] According to one embodiment of the present invention, the silica-based filler may be wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. As a specific example, the silica-based filler may be wet silica, which has the most remarkable effect of improving fracture characteristics and achieving wet grip. In addition, the silica-based filler may have a nitrogen adsorption surface area per gram (N2SA) of 120 m 2 / g to 180 m 2 / g, and the CTAB (cetyl trimethyl ammonium bromide) adsorption surface area is 100 m 2 / g to 200 m 2 / g, and within this range, the processability of the rubber composition can be excellent while sufficiently securing reinforcing performance by the filler.

[0138] According to one embodiment of the present invention, when a silica-based filler is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation properties. The above silane coupling agent is 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-dimethylthiocarbamoyltetrasulfide, 2-Triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-Trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-Triethoxysilylpropylbenzolyltetrasulfide, 3-Triethoxysilylpropylmethacrylate monosulfide, 3-Trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-Mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. As a specific example, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide when considering the effect of improving reinforcing properties.

[0139] 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 be specifically sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, and within this range, the required elastic modulus and strength of the vulcanized rubber composition can be secured, while at the same time ensuring low fuel consumption.

[0140] According to one embodiment of the present invention, the rubber composition may further include, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

[0141] According to one embodiment of the present invention, the vulcanization accelerator is not particularly limited, and specifically, thiazole compounds such as M(2-mercaptobenzothiazole), DM(dibenzothiazyl disulfide), CZ(N-cyclohexyl-2-benzothiazylsulfenamide), or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator can be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

[0142] According to one embodiment of the present invention, the process oil acts as a softener in the rubber composition, and specific examples thereof may be paraffinic, naphthenic, or aromatic compounds. More specifically, when considering tensile strength and wear resistance, an aromatic process oil may be used, and when considering hysteresis loss and low-temperature characteristics, a naphthenic or paraffinic process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, a decrease in tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber may be prevented.

[0143] 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 based on 100 parts by weight of the rubber component.

[0144] According to one embodiment of the present invention, the rubber composition can be obtained by mixing using a mixer such as a Banbury mixer, a roll mixer, or an internal mixer according to the above compounding prescription, and further, a rubber composition having low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding processing.

[0145] According to one embodiment of the present invention, the rubber composition may be useful in the manufacture of various components of a tire, such as a tire tread, undertread, sidewall, carcass coating rubber, belt coating rubber, bead filler, squeegee, or bead coating rubber, or various industrial rubber products, such as an anti-vibration rubber, a belt conveyor, or a hose. As a specific example, a molded product manufactured using the rubber composition may include a tire or a tire tread.

[0146]

[0147] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0148] Manufacturing Example 1

[0149] In a hexane solvent, NdV (neodymium versatate, Nd(2-ethyl hexanoate)3) and tri-n-octylaluminium (TNOA) were added and stirred at 0°C for 30 minutes to activate, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes to perform 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).

[0150]

[0151] Manufacturing Example 2

[0152] In a hexane solvent, NdV (neodymium versatate, Nd(2-ethyl hexanoate)3) and tri-n-octylaluminum (TNOA) were added and stirred at 0°C for 30 minutes to activate, triisobutylaluminum (TIBA) was added and stirred at 10°C for 30 minutes to perform 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).

[0153]

[0154] Manufacturing Example 3

[0155] In a hexane solvent, NdV (neodymium versatate, Nd(2-ethyl hexanoate)3) and triethylaluminum (TEAL) were added and activated by stirring at 0°C for 30 minutes, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes to perform 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).

[0156]

[0157] Manufacturing Example 4

[0158] In a hexane solvent, NdV (neodymium versatate, Nd(2-ethyl hexanoate)3) and triethylaluminum (TEAL) were added and stirred at 0°C for 30 minutes to activate, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes to perform 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).

[0159]

[0160] Manufacturing Example 5

[0161] In a hexane solvent, NdV (neodymium versatate, Nd(2-ethyl hexanoate)3) and triethylaluminum (TEAL) were added and stirred at 0°C for 30 minutes to activate, diisobutylaluminum hydride (DIBAH) was added and stirred at 10°C for 30 minutes to perform alkylation, and then aluminum sesquichloride (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).

[0162]

[0163] Comparative Manufacturing Example 1

[0164] In a hexane solvent, NdV (neodymium versatate, Nd(2-ethyl hexanoate)3) and diisobutyl aluminum hydride (DIBAH) were added and stirred at 10°C for 30 minutes to perform alkylation, and then diethyl aluminum 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).

[0165]

[0166] Comparative Manufacturing Example 2

[0167] In a hexane solvent, NdV (neodymium versatate, Nd(2-ethyl hexanoate)3) and triisobutyl aluminum (TIBA) were added and stirred at 10°C for 30 minutes to perform alkylation, and then diethyl aluminum 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).

[0168]

[0169] Examples and Comparative Examples

[0170] Example 1

[0171] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0172] While maintaining the first reactor at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Manufacturing 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 conducted for 90 minutes. When the polymerization conversion rate was 80% or higher, the reactor was transferred to the second reactor maintained at 80°C, and polymerization was further conducted for 15 minutes. Thereafter, the reaction was 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, and the solvent was removed by steam stripping and dried using a hot roll to prepare a conjugated diene polymer.

[0173]

[0174] Example 2

[0175] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0176] While maintaining the first reactor at 85°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Manufacturing 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 conducted for 110 minutes. When the polymerization conversion rate was 80% or higher, the reactor was transferred to the second reactor maintained at 85°C, and polymerization was further conducted for 15 minutes. Thereafter, the reaction was 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, and the solvent was removed by steam stripping and dried using a hot roll to prepare a conjugated diene polymer.

[0177]

[0178] Example 3

[0179] In Example 1, a conjugated diene polymer was manufactured in the same manner as in Example 1, except that the catalyst composition manufactured in Manufacturing Example 3 (0.05 mmol / 100 g of 1,3-butadiene based on NdV in the catalyst composition) was used as the catalyst composition.

[0180]

[0181] Example 4

[0182] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0183] While maintaining the first reactor at 85°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Manufacturing 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 performed for 110 minutes. When the polymerization conversion rate was 80% or higher, the mixture was transferred to the second reactor maintained at 85°C. At this time, 7 kg / hr of 1,3-butadiene was additionally introduced into the second reactor, and polymerization was performed for an additional 15 minutes. Meanwhile, 70 wt% of the total 1,3-butadiene used in the polymer was introduced into the first reactor, and the remaining 30 wt% was introduced into the second reactor. The catalyst composition was based on the total amount of 1,3-butadiene used in the polymer. Afterwards, the reaction was 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 through steam stripping, and the conjugated diene polymer was manufactured by drying using a hot roll.

[0184]

[0185] Example 5

[0186] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0187] While maintaining the first reactor at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Manufacturing 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 conducted for 60 minutes. When the polymerization conversion rate was 80% or higher, the reactor was transferred to the second reactor maintained at 90°C, and polymerization was further conducted for 15 minutes. Thereafter, the reaction was 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, and the solvent was removed by steam stripping and dried using a hot roll to prepare a conjugated diene polymer.

[0188]

[0189] Example 6

[0190] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0191] While maintaining the first reactor at 75°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Manufacturing 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 performed for 110 minutes. When the polymerization conversion rate was 80% or higher, the mixture was transferred to the second reactor maintained at 80°C. At this time, 7 kg / hr of 1,3-butadiene was additionally introduced into the second reactor, and polymerization was performed for an additional 15 minutes. Meanwhile, 70 wt% of the total 1,3-butadiene used in the polymer was introduced into the first reactor, and the remaining 30 wt% was introduced into the second reactor. The catalyst composition was based on the total amount of 1,3-butadiene used in the polymer. Afterwards, the reaction was 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 through steam stripping, and the conjugated diene polymer was manufactured by drying using a hot roll.

[0192]

[0193] Comparative Example 1

[0194] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0195] While maintaining the first reactor at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Comparative Manufacturing 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 conducted for 60 minutes. When the polymerization conversion rate was 80% or higher, the reactor was transferred to the second reactor maintained at 80°C, and polymerization was further conducted for 15 minutes. Thereafter, the reaction was 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, and the solvent was removed by steam stripping and dried using a hot roll to prepare a conjugated diene polymer.

[0196]

[0197] Comparative Example 2

[0198] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0199] While maintaining the first reactor at 80°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Comparative Manufacturing 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 conducted for 60 minutes. When the polymerization conversion rate was 80% or higher, the reactor was transferred to the second reactor maintained at 80°C, and polymerization was further conducted for 15 minutes. Thereafter, the reaction was 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, and the solvent was removed by steam stripping and dried using a hot roll to prepare a conjugated diene polymer.

[0200]

[0201] Comparative Example 3

[0202] A conjugated diene polymer was produced using a polymerization reactor in which two 80 L stainless steel reactors equipped with a stirrer and a jacket were connected in series.

[0203] While maintaining the first reactor at 75°C, 35 kg / h of hexane, 7 kg / hr of 1,3-butadiene, and the catalyst composition prepared in Manufacturing 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 conducted for 60 minutes. When the polymerization conversion rate was 80% or higher, the reactor was transferred to the second reactor maintained at 80°C, and polymerization was further conducted for 15 minutes. Thereafter, the reaction was 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, and the solvent was removed by steam stripping and dried using a hot roll to prepare a conjugated diene polymer.

[0204]

[0205] Experimental example

[0206] Experimental Example 1

[0207] For the conjugated diene polymers manufactured in Examples 1 to 6 and Comparative Examples 1 to 3, viscoelasticity analysis was performed according to Mooney viscosity, molecular weight distribution, cis-1,4 bond content, and frequency change, as follows, and the results are shown in Table 1 below.

[0208] * Mooney viscosity (ML1+4, @100℃): For each polymer, Mooney viscosity was measured at 100℃ using a Monsanto MV2000E Large Rotor, with a rotor speed of 2±0.02 rpm. The sample was left at room temperature (23±3℃) for more than 30 minutes, and then 27±3 g was collected and filled into the die cavity. The platen was operated to apply torque while Mooney viscosity was measured.

[0209]

[0210] * 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, then loaded onto a gel permeation chromatography (GPC) column and run. At this time, two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories were used in combination. In addition, all newly replaced columns were mixed-bed type columns, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

[0211]

[0212] * Cis-1,4 bond content (wt%): The cis-1,4 bond content of the conjugated diene moiety was measured by Fourier transform infrared spectroscopy (FT-IR). Specifically, the FT-IR transmittance spectrum of the carbon disulfide solution of the conjugated diene polymer prepared at a concentration of 5 mg / mL using carbon disulfide in the same cell as a blank was measured, and then the 1130 cm of the measured spectrum -1 The maximum peak value near (a, baseline) is 967 cm, indicating a trans-1,4 bond. -1 The minimum peak value near (b) is 911 cm, indicating vinyl bonding. -1 The minimum peak value (c) near 736 cm, indicating a cis-1,4 bond. -1 Each content was obtained using the minimum peak value (d) in the vicinity.

[0213]

[0214] * Viscoelasticity analysis according to frequency change: Using a DHR-2 rheometer from TA Instruments and a parallel plate with a diameter of 8 mm, measurements were made at 120℃, 0.1% strain, and at an angular frequency of 0.01 rad / s to 100 rad / s. The Tan δ graph for frequency (Hz) obtained from the measurements was the difference between the maximum and minimum values ​​of the phase angle confirmed in the angular frequency of 0.01 rad / s to 100 rad / s (Max-Min), the maximum value of the phase angle confirmed in the angular frequency of 0.01 rad / s to 100 rad / s (Max), the difference between the phase angle at 1 rad / s and 0.1 rad / s (PA@1 rad / s - PA@0.1 rad / s), and the difference between the phase angle at 0.01 rad / s and 0.1 rad / s (PA@0.1 rad / s - PA@0.1 rad / s) at an angular frequency of 0.01 The complex viscosity in rad / s was confirmed. At this time, the sample was prepared by placing approximately 5 g of polymer between parallel plates, setting the gap between the parallel plates to 1 mm, and removing any polymer that escaped to the outside before use.

[0215]

[0216] Through the above Table 1, it was confirmed that the conjugated diene polymers of Examples 1 to 6 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, a maximum value (Max) of the phase angle of 44° or less, a difference (PA@1 rad / s - PA@0.1 rad / s) between the phase angle at 1 rad / s and the phase angle at 0.1 rad / s of 1 rad / s or more, and a complex viscosity at 0.01 rad / s of 180,000 Pa.s or more, thereby satisfying the properties presented in the present invention.

[0217]

[0218] Experimental Example 2

[0219] After manufacturing a rubber composition and a rubber specimen using the conjugated diene polymer manufactured in Examples 1 to 6 and Comparative Examples 1 to 3, the Mooney viscosity, tensile properties, viscoelastic properties, and wear resistance of the rubber composition were measured using the following method, and the results are shown in Table 2 below.

[0220]

[0221] <Manufacture of rubber composition and rubber specimen>

[0222] Each rubber composition was prepared by mixing 100 parts by weight of each of the conjugated diene polymers of Examples 1 to 6 and Comparative Examples 1 to 3 with 60 parts by weight of carbon black, 15 parts by weight of process oil (TDAT oil), 3 parts by weight of zinc oxide (ZnO), and 2 parts by weight of stearic acid.

[0223] Thereafter, 1.5 parts by weight of sulfur and 0.9 parts by weight of a vulcanization accelerator (TBBS) were added to each of the above rubber compositions, gently mixed at 50 rpm for 2 minutes at 50°C, and then a sheet-shaped vulcanized mixture was obtained using a 50°C roll. The obtained vulcanized mixture was vulcanized at 160°C for 20 minutes to prepare a rubber specimen.

[0224]

[0225] * Mooney viscosity (ML1+4, @100℃): For each rubber composition, Mooney viscosity was measured at 100℃ with a large rotor of Monsanto MV2000E at a rotor speed of 2±0.02 rpm. The sample used was left at room temperature (23±3℃) for more than 30 minutes, then 27±3 g was collected and filled into the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen. In addition, the difference (△MV) between the Mooney viscosity of the measured rubber composition and the Mooney viscosity of the conjugated diene polymer measured in Experimental Example 1 was calculated.

[0226] In addition, the measured value of Comparative Example 1 was used as a reference value, and the difference in Mooney viscosity of each example and comparative example was indexed using Equation 1 below, and the processability was confirmed with this value, with a larger value indicating better processability.

[0227] [Formula 1]

[0228] Processability = {[(reference value - measured value) / reference value] × 100} + 100

[0229]

[0230] * Tensile properties: Each rubber composition manufactured above was vulcanized at 150℃ for t90 minutes, and the modulus at 300% elongation of the vulcanized product (M-300%, kg·f / cm) was measured according to ASTM D412. 2) was measured. The measured value of Comparative Example 1 was used as the reference value, and the 300% modulus of each example and comparative example was indexed using Equation 2 below. A larger value indicates better performance.

[0231] [Formula 2]

[0232] M-300% Index = (Measured value / Reference value) × 100

[0233]

[0234] * Viscoelastic properties: Using DMTS 500N from Gabo, Germany, the viscoelastic coefficient (Tanδ) was measured at a frequency of 10 Hz, a prestrain of 3%, and a dynamic strain of 3% at temperatures from -60°C to 60°C. The Tanδ value at 60°C represents the rolling resistance characteristics (fuel efficiency). The measured values ​​of Comparative Example 1 were used as reference values, and the viscoelastic properties of each example and comparative example were indexed using the following equation 3.

[0235] [Formula 3]

[0236] Tan δ @ 60℃ Index = {[(reference value-measured value) / reference value]×100}+100

[0237]

[0238] * Abrasion resistance: For each rubber specimen manufactured above, a DIN abrasion test was performed in accordance with ASTM D5963, and the results were expressed as DIN wt loss index (loss volume index: ARIA (Abrasion resistance index, Method A)). The measured value of Comparative Example 1 was used as the reference value, and the abrasion resistance of each example and comparative example was indexed using Equation 4 below.

[0239] [Formula 4]

[0240] Wear Index = {[(reference value - measured value) / reference value] × 100} + 100

[0241]

[0242] As shown in Table 2 above, Examples 1 to 6 showed improved wear resistance and significantly increased processability while maintaining the same tensile properties and viscoelastic properties as Comparative Examples 1 to 3.

[0243]

[0244] From these results, it was confirmed that the conjugated diene polymer of the present invention exhibits improved processability while maintaining the physical properties of the conjugated diene polymer, except for processability, at the level of a highly linear conjugated diene polymer by introducing a branch into the linear conjugated diene polymer, and while maintaining the mixing properties in the rubber composition at a high level.

Claims

1. Contains a conjugated diene monomer unit, The cis bond content is 95.0 wt% or more, A conjugated diene polymer in which 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 when a dynamic viscoelasticity analysis is performed according to a change in frequency.

2. In paragraph 1, A conjugated diene polymer having a maximum value (Max) of a phase angle of 44° or less in the angular frequency range of 0.01 rad / s to 100 rad / s when dynamic viscoelasticity analysis is performed according to frequency change.

3. In paragraph 1, A conjugated diene polymer in which the difference between the phase angle at an angular frequency of 1 rad / s and the phase angle at 0.1 rad / s (PA@1 rad / s - PA@0.1 rad / s) is +1.7° or more when a dynamic viscoelasticity analysis is performed according to a change in frequency.

4. In paragraph 1, A conjugated diene polymer having a complex viscosity of 180,000 Pa.s or more at an angular frequency of 0.01 rad / s when dynamic viscoelasticity analysis is performed according to frequency change.

5. In paragraph 1, The above conjugated diene polymer is a conjugated diene polymer containing a branched chain.

6. In paragraph 1, A conjugated diene polymer having a number average molecular weight of 200,000 g / mol or more and 400,000 g / mol or less.

7. In paragraph 1, A conjugated diene polymer having a weight average molecular weight of 500,000 g / mol or more and 800,000 g / mol or less.

8. In paragraph 1, A conjugated diene polymer having a molecular weight distribution of 2.0 or more and 3.0 or less.

9. In paragraph 1, A conjugated diene polymer having a Mooney viscosity (ML1+4 @100℃) of 40 or more and 65 or less.

10. A rubber composition comprising a conjugated diene polymer according to any one of claims 1 to 9.

Images