Method for producing catalyst composition and method for producing conjugated diene polymer

Abstract

The present invention relates to a method for preparing a catalyst composition and a method for preparing a conjugated diene-based polymer using the catalyst composition prepared thereby, the preparation method of the catalyst composition continuously prepares a catalyst composition having improved catalyst activity by pretreating a hydrogen bond type lanthanide rare earth element compound and / or an oligomer type lanthanide rare earth element compound that causes deterioration of catalyst activity.

Description

[0001] Cross - reference to related applications

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10 - 2023 - 0082987, filed on June 27, 2023, the entire content of which is incorporated herein by reference. Technical field

[0003] The present invention relates to a method for preparing a catalyst composition for preparing a conjugated diene polymer, and a method for preparing a conjugated diene polymer using the same. Background art

[0004] Recently, with the increasing attention to energy conservation and environmental issues, there is a need to reduce the fuel consumption rate of automobiles. As a method for achieving this demand, a method has been proposed to increase the cis - bond content and linearity of polybutadiene in a rubber composition for tire formation while reducing the molecular weight distribution.

[0005] Polybutadiene can be prepared using a Ziegler - Natta catalyst, which is prepared by activating an organic acid metal compound with an alkyl aluminum and an alkyl aluminum halide compound, and the prepared catalyst reacts with 1,3 - butadiene monomer to prepare polybutadiene.

[0006] Here, the organic acid metal compounds include titanium - based, nickel - based, cobalt - based, and lanthanum - based compounds. Considering increasing the cis - bond content and linearity of polybutadiene and reducing the molecular weight distribution, lanthanide rare - earth element compounds are mainly used.

[0007] Examples of lanthanide rare - earth element compounds include neodymium - based compounds, specifically neodymium versatate (NdV). The lanthanide rare - earth element compounds can be activated by alkylation using an alkyl aluminum compound and then halogenation using an alkyl aluminum halide compound, and in order to stabilize the catalyst, 1,3 - butadiene monomer can be injected during alkylation for pre - formation.

[0008] In this case, lanthanide rare - earth element compounds such as NdV do not exist as a single compound type, but exist in a hydrogen - bond type and / or oligomer type through moisture and aliphatic compounds used in the preparation process (Non - Patent Document 1 and Non - Patent Document 2). However, if the hydrogen - bond type lanthanide rare - earth element compounds and / or oligomer type lanthanide rare - earth element compounds are immediately alkylated, compared with the case where the lanthanide rare - earth element compounds exist as a single compound, alkylation takes a longer time, and there is a problem that alkylation cannot be sufficiently carried out. If the lanthanide rare - earth element compounds with insufficient alkylation are injected into a halogenation reactor for halogenation, it may be a factor leading to deterioration of catalyst activity, and there may be a problem of increasing the pollution of catalyst preparation equipment.

[0009] U.S. Patent Publication No. 9,056,303 (Patent Document 1) discloses a method for manufacturing a catalyst system using multiple alkylation reactors. In the case of continuous preparation to address the defects in the batch - type manufacture of the catalyst system, Patent Document 1 specifically specifies the type of reactor and controls the output flux of the catalyst system at the pipeline outlet to the required degree to maintain within an appropriate residence time range for alkylation and chlorination, thereby preventing the formation of gels in the reactor and ensuring the flexibility of the alkylating agent and the salts of rare - earth elements that may affect the degree of catalyst activity. Additionally, Japanese Patent Publication No. 5,072,191 (Patent Document 2) discloses a method for preparing a catalyst for polymerizing conjugated dienes, including sequentially injecting an alkylaluminum compound and an alkylaluminum hydride. However, in Patent Documents 1 and 2, during the preparation of the catalyst system and the catalyst for polymerizing conjugated dienes, only the lanthanide compound is directly alkylated, without recognizing the type of the injected lanthanide compound and its resulting impact on the catalyst activity.

[0010] [Prior Art Documents]

[0011] [Patent Documents]

[0012] (Patent Document 1) US 9056303 B2

[0013] (Patent Document 2) JP 5072191 B2

[0014] [Non - Patent Documents]

[0015] (Non - Patent Document 1) "A Highly Reactive and Monomeric Neodymium Catalyst", Macromolecules 2002, 35, 13, 4875 - 4879 (https: / / doi.org / 10.1021 / ma012123p)

[0016] (Non - Patent Document 2) "Living and non - living Ziegler - Natta catalysts: electronic properties of active site", Polymer, Vol. 44, No. 21, October 2003, pp. 6555 - 6558 (https: / / doi.org / 10.1016 / S0032 - 3861(03)00698 - 0) Summary of the Invention

[0017] Technical Problem

[0018] The task to be solved by the present invention is to improve the catalyst activity in the continuous preparation of a catalyst composition for polymerizing polybutadiene by pretreating a hydrogen-bonded lanthanide rare earth element compound and / or an oligomer-type lanthanide rare earth element compound that causes deterioration of the catalyst activity before alkylation.

[0019] That is, in order to solve the defects described in the background art of the present invention, the object of the present invention is to provide a method for continuously preparing a catalyst composition with improved catalyst activity by pre-treating a hydrogen-bonded lanthanide rare earth element compound and / or an oligomer-type lanthanide rare earth element compound that causes deterioration of the catalyst activity.

[0020] In addition, another object of the present invention is to provide a method for preparing a conjugated diene polymer with a high cis bond content, high linearity, and a narrow molecular weight distribution by using the catalyst composition prepared by the above method for preparing the catalyst composition.

[0021] Technical solution

[0022] To solve the above tasks, the present invention provides a method for preparing a catalyst composition and a method for preparing a conjugated diene polymer.

[0023] (1) The present invention provides a method for preparing a catalyst composition, which includes: a step (S10) of performing a pretreatment reaction on a lanthanide rare earth element compound in the form of a hydrogen bond, an oligomer, or a combination thereof; an alkylation step (S20) of mixing and reacting the lanthanide rare earth element compound pretreated in the form of a hydrogen bond, an oligomer, or a combination thereof in step (S10) with an alkylating agent; and a halogenation step (S30) of mixing and reacting the alkylated lanthanide rare earth element compound in step (S20) with a halogen compound, wherein the step (S10) is carried out by mixing and reacting the lanthanide rare earth element compound with one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, and the step (S10), the step (S20), and the step (S30) are each carried out in separate reactors connected in series.

[0024] (2) The present invention provides the method for preparing a catalyst composition according to (1), wherein the step (S10) is carried out before the lanthanide rare earth element compound is alkylated by the trialkylaluminum.

[0025] (3) The present invention provides the method for preparing a catalyst composition according to (1) or (2), wherein the lanthanide rare earth element compound is a neodymium compound represented by formula 1.

[0026] [Formula 1]

[0027]

[0028] In Formula 1, R 1 to R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, where R 1 to R 3 are not all hydrogen.

[0029] (4) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (3), wherein the lanthanide rare earth element compound is selected from the group consisting of Nd(2-ethylhexanoate) 3 , Nd(2,2-dimethyldecanoate) 3 , Nd(2,2-diethyldecanoate) 3 , Nd(2,2-dipropyldecanoate) 3 , Nd(2,2-dibutyldecanoate) 3 , Nd(2,2-dihexyldecanoate) 3 , Nd(2,2-dioctyldecanoate) 3 , Nd(2-ethyl-2-propyldecanoate) 3 , Nd(2-ethyl-2-butyldecanoate) 3 , Nd(2-ethyl-2-hexyldecanoate) 3 , Nd(2-propyl-2-butyldecanoate) 3 , Nd(2-propyl-2-hexyldecanoate) 3 , Nd(2-propyl-2-isopropyldecanoate) 3 , Nd(2-butyl-2-hexyldecanoate) 3 , Nd(2-hexyl-2-octyldecanoate) 3 , Nd(2,2-diethylcaprylate) 3 , Nd(2,2-dipropylcaprylate) 3 , Nd(2,2-dibutylcaprylate) 3 , Nd(2,2-dihexylcaprylate) 3 , Nd(2-ethyl-2-propylcaprylate) 3 , Nd(2-ethyl-2-hexylcaprylate) 3 , Nd(2,2-diethylnonanoate) 3 , Nd(2,2-dipropylnonanoate) 3 , Nd(2,2-dibutylnonanoate) 3 , Nd(2,2-dihexylnonanoate) 3 , Nd(2-ethyl-2-propylnonanoate) 3 and Nd(2-ethyl-2-hexylnonanoate) 3 and more than one of the group consisting of.

[0030] (5) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (4), wherein the alkylating agent is an alkylaluminum compound represented by Formula 2.

[0031] [Formula 2]

[0032] AlR 4 R 5 R 6

[0033] In Formula 2, R 4 to R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein R 4 to R 6 are not all hydrogen, and do not include tri-n-hexylaluminum and tri-n-octylaluminum.

[0034] (6) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (5), wherein the alkylating agent is dialkylaluminum hydride.

[0035] (7) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (6), wherein the pretreatment reaction in step (S10), the alkylation in step (S20), or the pretreatment reaction in step (S10) and the alkylation in step (S20) are carried out by including a conjugated diene monomer.

[0036] (8) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (7), wherein the halogen compound is one or more selected from the group consisting of an alkylaluminum halide represented by Formula 3 and an alkylaluminum sesquihalide represented by Formula 4.

[0037] [Formula 3]

[0038] AlR 7 R 8 R 9

[0039] In Formula 3, R 7 to R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, wherein R 7 to R 9 are not all halogen groups.

[0040] [Formula 4]

[0041]

[0042] In Formula 4, R 10 to R 12 are each independently an alkyl group having 1 to 12 carbon atoms, and X1 to X 3 Each independently represents a halogen group.

[0043] (9) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (8), wherein the halogen compound is one or more selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides.

[0044] (10) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (9), wherein the step (S20) is continuously carried out in a plurality of reactors connected in series.

[0045] (11) The present invention provides a method for preparing a catalyst composition according to (10), wherein the alkylating agent is separately injected into the plurality of reactors connected in series.

[0046] (12) The present invention provides a method for preparing a catalyst composition according to any one of (1) to (11), wherein the step (S10), the step (S20), and the step (S30) are continuously carried out.

[0047] (13) The present invention provides a method for preparing a conjugated diene polymer, which includes a step (S100) of polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition prepared by the method for preparing a catalyst composition according to any one of (1) to (12) to prepare a living polymer.

[0048] (14) The present invention provides a conjugated diene polymer prepared by the method for preparing a conjugated diene polymer according to (13).

[0049] (15) The present invention provides a rubber composition containing the conjugated diene polymer according to (14).

[0050] Advantageous Effects

[0051] The catalyst composition prepared by the method for preparing a catalyst composition according to the present invention is prepared by pretreating a hydrogen-bonded lanthanide rare earth element compound and / or an oligomeric lanthanide rare earth element compound that cause deterioration of catalyst activity before alkylation, and has excellent catalyst activity.

[0052] According to the method for preparing a catalyst composition of the present invention, a catalyst composition can be continuously prepared, and the productivity of the catalyst composition and the conjugated diene polymer using the same can be improved, and more uniform quality can be ensured.

[0053] The conjugated diene polymer prepared by the method for preparing a conjugated diene polymer according to the present invention has a low content of lanthanide rare earth elements remaining in the conjugated diene polymer due to high catalyst activity, a high content of cis bonds and linearity, a narrow molecular weight distribution, and when applied to a rubber composition, can exhibit excellent abrasion resistance and a low fuel consumption rate. Detailed Description

[0054] Hereinafter, the present invention will be described in more detail to assist in understanding the present invention.

[0055] It will be understood that the words or terms used in the specification and claims of the present invention should not be construed as having the meanings defined in a common dictionary. It will be further understood that, based on the principle that the inventor can appropriately define the meanings of words or terms to best explain the present invention, the words or terms should be construed as having meanings consistent with the meaning of the technical idea of the present invention.

[0056] Preparation method of catalyst composition

[0057] The present invention provides a method for preparing a catalyst composition. The catalyst composition prepared by the method for preparing the catalyst composition can be a catalyst composition for polymerizing a conjugated diene polymer.

[0058] According to an embodiment of the present invention, the method for preparing a catalyst composition may include: a step (S10) of performing a pretreatment reaction of a lanthanide rare earth element compound in a hydrogen bond type, oligomer type, or a combination thereof; an alkylation reaction step (S20) of mixing and reacting the lanthanide rare earth element compound pretreated in the hydrogen bond type, oligomer type, or a combination thereof in step (S10) with an alkylating agent; and a halogenation step (S30) of mixing and reacting the alkylated lanthanide rare earth element compound in step (S20) with a halogen compound, and the step (S10) may be performed by mixing and reacting the lanthanide rare earth element compound with one or more trialkyl aluminums selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum, and the step (S10), the step (S20), and the step (S30) may be performed in separate reactors connected in series.

[0059] As described in the background art of the present invention, lanthanide rare earth element compounds do not exist as a single compound type, but exist in the form of hydrogen bond type and / or oligomer type through moisture and aliphatic compounds used in the preparation process (see Non-Patent Document 1 and Non-Patent Document 2). However, if the hydrogen bond type lanthanide rare earth element compound and / or oligomer type lanthanide rare earth element compound are immediately alkylated, compared with the case where the lanthanide rare earth element compound exists as a single compound, the alkylation requires a longer time, and there is a problem that the alkylation cannot be sufficiently carried out. If the lanthanide rare earth element compound with insufficient alkylation is injected into a halogenation reactor for halogenation, it may be a factor causing deterioration of the catalyst activity, and there may be a problem of increasing the contamination of the catalyst preparation equipment. However, in the method for preparing the catalyst composition of the present invention, the hydrogen bond type lanthanide rare earth element compound and / or oligomer type lanthanide rare earth element compound are pretreated according to step (S10) before alkylation, and the catalyst activity can be improved. Here, the pretreatment may refer to minimizing and further removing the hydrogen bond type lanthanide rare earth element compound and / or oligomer type lanthanide rare earth element compound before alkylation.

[0060] According to an embodiment of the present invention, step (S10) can be carried out by mixing and reacting a lanthanide rare earth element compound with one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum. It is known that tri-n-hexylaluminum and tri-n-octylaluminum can be used as alkylating agents for alkylation. However, if tri-n-hexylaluminum and tri-n-octylaluminum are not used for the pretreatment of step (S10) as in the present invention, but simply used as alkylating agents, the lanthanide rare earth element compound may only cause alkylation according to this purpose, which requires a long time for alkylation and causes the defect of insufficient alkylation. In this regard, step (S10) can be carried out until the time point just before one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum start to alkylate the lanthanide rare earth element compound. At the same time, trialkylaluminum and / or dialkylaluminum hydride that can be used as alkylating agents other than tri-n-hexylaluminum and tri-n-octylaluminum may be insufficient to cause pretreatment of the hydrogen bond type, oligomer type or a combination thereof of the lanthanide rare earth element compound, and may not be suitable as the trialkylaluminum compound for the pretreatment of step (S10).

[0061] According to an embodiment of the present invention, step (S10) can be carried out by injecting more than 1 mol, more than 2 mol, more than 3 mol, more than 4 mol, more than 5 mol, more than 6 mol, more than 7 mol, more than 8 mol, more than 9 mol, or more than 10 mol and less than 20 mol, less than 19 mol, less than 18 mol, less than 17 mol, less than 16 mol, less than 15 mol, less than 14 mol, less than 13 mol, less than 12 mol, less than 11 mol, or less than 10 mol of at least one trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum relative to 1 mol of the lanthanide rare earth element compound.

[0062] According to an embodiment of the present invention, step (S10) can be carried out at a temperature of -20 °C or higher, -15 °C or higher, or -10 °C or higher and at a temperature of 40 °C or lower, 35 °C or lower, 30 °C or lower, 25 °C or lower, or 20 °C or lower.

[0063] According to an embodiment of the present invention, step (S10) can be carried out for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more and 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0064] According to an embodiment of the present invention, by controlling the molar ratio of the lanthanide rare earth element compound to at least one trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, the reaction temperature, and the reaction time, the efficiency of the pretreatment of the lanthanide rare earth element compound in the form of hydrogen bond type, oligomer type, or a combination thereof in step (S10) can be further improved.

[0065] According to one embodiment of the present invention, the lanthanide rare earth element compound may be a neodymium compound. Specifically, neodymium carboxylates (such as 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 (such as 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, neodymium didecyl phosphate, etc.); organic phosphonates (such as neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium decylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, etc.); organic hypophosphites (such as neodymium butylhypophosphite, neodymium pentylhypophosphite, neodymium hexylhypophosphite, neodymium heptylhypophosphite, neodymium octylhypophosphite, neodymium (1-methylheptyl)hypophosphite, neodymium (2-ethylhexyl)hypophosphite, etc.); carbamates (such as neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, neodymium dibenzylcarbamate, etc.); dithiocarbamates (such as neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate, etc.); xanthates (such as neodymium methylxanthate, neodymium ethylxanthate, neodymium isopropylxanthate, neodymium butylxanthate, neodymium benzylxanthate, etc.); β-diketonates (such as neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylacetonate, etc.); alkoxides or allyloxides (such as neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide, neodymium nonylphenoxide, etc.); halides or pseudohalides (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide, etc.); oxyhalides (such as neodymium oxyfluoride, neodymium oxychloride, neodymium oxybromide, etc.); or organoneodymium compounds containing more than one rare earth element-carbon bond (such as Cp 3 Ln, Cp 2 LnR, Cp 2 LnCl, CpLnCl 2 , CpLn(cyclooctatetraene), (C 5 Me 5 ) 2 LnR, LnR 3 , Ln(allyl) 3 , Ln(allyl) 2 Cl, etc., where Ln is a rare earth metal element and R is a hydrocarbon group), and may include any one or a mixture of two or more thereof.

[0066] According to one embodiment of the present invention, the lanthanide rare earth element compound may be a neodymium compound represented by Formula 1.

[0067] [Formula 1]

[0068]

[0069] In Formula 1, R 1 to R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein R 1 to R 3 are not all hydrogen. In a specific embodiment, in Formula 1, R 1 can be an alkyl group having 4 to 12 carbon atoms, and R 2 and R 3 can each independently be hydrogen or an alkyl group having 1 to 8 carbon atoms, wherein R 2 and R 3 are not all hydrogen. In a more specific embodiment, in Formula 1, R 1 can be an alkyl group having 6 to 8 carbon atoms, and R 2 and R 3 can each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R 2 and R 3 are not all hydrogen.

[0070] According to an embodiment of the present invention, the lanthanide rare earth element compound can be selected from the group consisting of Nd(2-ethylhexanoate) 3 , neodymium versatate, Nd(2,2-dimethyldecanoate) 3 , Nd(2,2-diethyldecanoate) 3 , Nd(2,2-dipropyldecanoate) 3 , Nd(2,2-dibutyldecanoate) 3 , Nd(2,2-dihexyldecanoate) 3 , Nd(2,2-dioctyldecanoate) 3 , Nd(2-ethyl-2-propyldecanoate) 3 , Nd(2-ethyl-2-butyldecanoate) 3 , Nd(2-ethyl-2-hexyldecanoate) 3 , Nd(2-propyl-2-butyldecanoate) 3 , Nd(2-propyl-2-hexyldecanoate) 3 , Nd(2-propyl-2-isopropyldecanoate) 3 , Nd(2-butyl-2-hexyldecanoate) 3 , Nd(2-hexyl-2-octyldecanoate) 3 , Nd(2,2-diethyloctanoate) 3 , Nd(2,2-dipropyloctanoate) 3, Nd(2,2-dibutyloctanoate) 3 , Nd(2,2-dihexyloctanoate) 3 , Nd(2-ethyl-2-propyl octanoate) 3 , Nd(2-ethyl-2-hexyl octanoate) 3 , Nd(2,2-diethylnonanoate) 3 , Nd(2,2-dipropylnonanoate) 3 , Nd(2,2-dibutylnonanoate) 3 , Nd(2,2-dihexylnonanoate) 3 , Nd(2-ethyl-2-propylnonanoate) 3 and one or more selected from the group consisting of Nd(2-ethyl-2-hexylnonanoate) 3 .

[0071] According to one embodiment of the present invention, the neodymium compound may include a carboxylate ligand including a substituent having two or more different-length alkyl groups at the α-position, causing a steric change around the neodymium central metal to prevent the entanglement phenomenon between the compounds. Therefore, the effect of suppressing oligomerization can be achieved during the polymerization of conjugated diene polymers using the catalyst composition. In addition, such a neodymium-based compound has a high solubility in a solvent, and the ratio of neodymium that is difficult to be converted into a catalyst active species located in the central part is reduced. Therefore, an effect of achieving a high conversion rate to the catalyst active species can be shown.

[0072] According to one embodiment of the present invention, at room temperature (25 °C), the solubility of the neodymium compound may be about 60 parts by weight or more with respect to 100 parts by weight of the non-polar solvent. The solubility of the neodymium compound refers to the degree of clear dissolution without turbidity, and by showing such a high solubility, excellent catalyst activity can be shown.

[0073] According to one embodiment of the present invention, step (S10) may be carried out by including a conjugated diene monomer. The conjugated diene monomer used in the polymerization of conjugated diene polymers using the catalyst composition prepared according to the present invention is pre-mixed with the catalyst composition to form a pre-polymerized pre-formed or pre-mixed catalyst composition, thereby further improving the activity of the catalyst composition. In addition, the active polymer thus prepared can be stabilized. "Preforming" may refer to adding a small amount of a conjugated diene monomer such as 1,3-butadiene to reduce the possibility of generation of various active species of the catalyst composition in the catalyst system, and the pre-polymerization in the catalyst composition system is carried out together with the addition of 1,3-butadiene. In addition, "pre-mixing" may refer to a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

[0074] According to an embodiment of the present invention, the conjugated diene monomer that can be injected in step (S10) may be 1,3-butadiene or its derivatives such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 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, etc.

[0075] According to an embodiment of the present invention, if step (S10) is carried out by including a conjugated diene monomer, then relative to 1 mol of the lanthanide rare earth element compound, 1 mol or more, 5 mol or more, 10 mol or more, 15 mol or more, or 20 mol or more and 100 mol or less, 90 mol or less, 80 mol or less, 70 mol or less, 60 mol or less, or 50 mol or less of the conjugated diene monomer can be injected.

[0076] According to an embodiment of the present invention, step (S20) is a step of alkylating the lanthanide rare earth element compound, and it can be carried out by mixing and reacting the pre-treated lanthanide rare earth element compound of the hydrogen bond type, oligomer type, or a combination thereof with an alkylating agent.

[0077] According to an embodiment of the present invention, the alkylating agent may be an organometallic compound, which can transfer a hydrocarbon group to other metals and can act as a co-catalyst. The alkylating agent may be an organometallic compound that is soluble in a polymer solvent and contains a metal-carbon bond, such as an organoaluminum compound, an organomagnesium compound, and an organolithium compound.

[0078] According to an embodiment of the present invention, the alkylating agent may be an organoaluminum compound. Specifically, it may be alkylaluminum, such as tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum; dihydrocarbylaluminum hydride, 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, phenylethylaluminum 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; hydrocarbylaluminum dihydride, such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

[0079] According to an embodiment of the present invention, considering controlling the catalytic reaction and side reactions of the pre-treated lanthanide rare earth element compound in the form of hydrogen bond type, oligomer type or a combination thereof in step (S10), the alkylating agent may preferably be an alkylaluminum compound. In a specific embodiment, the alkylating agent may be the alkylaluminum compound represented by Formula 2.

[0080] [Formula 2]

[0081] AlR 4 R 5 R 6

[0082] In Formula 2, R 4 to R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein R 4 to R 6 are not all hydrogen, and do not include tri-n-hexylaluminum and tri-n-octylaluminum. In a specific embodiment, in Formula 2, R 4 to R 6 may each independently be hydrogen or an alkyl group having 3 to 8 carbon atoms, wherein R 4 to R 6 are not all hydrogen, and do not include tri-n-hexylaluminum and tri-n-octylaluminum. 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, wherein R 4 to R 6They may not all be hydrogen, and do not include tri-n-hexylaluminum and tri-n-octylaluminum.

[0083] According to an embodiment of the present invention, considering controlling the catalytic reaction and side reactions of the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof in step (S10), the alkylating agent may be dialkylaluminum hydride, and the type of the dialkylaluminum hydride is the same as described above. In a specific embodiment, the alkylating agent may be diisobutylaluminum hydride.

[0084] According to an 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 the group consisting of dialkylaluminum hydride and trialkylaluminum. 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.

[0085] According to an embodiment of the present invention, step (S20) may be carried out by injecting 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 and 30 mol or less, 29 mol or less, 28 mol or less, 27 mol or less, 26 mol or less, 25 mol or less, 24 mol or less, 23 mol or less, 22 mol or less, 21 mol or less, 20 mol or less, 19 mol or less, 18 mol or less, 17 mol or less, 16 mol or less, 15 mol or less of the alkylating agent relative to 1 mol of the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof in step (S10).

[0086] According to an embodiment of the present invention, step (S20) may be carried out at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher and at a temperature of 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, or 20°C or lower.

[0087] According to an embodiment of the present invention, step (S20) may be carried out for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more and 2 hours or less, 1 hour 30 minutes or less, 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0088] According to an embodiment of the present invention, by controlling the molar ratio, reaction temperature, and reaction time of the pre-treated lanthanide rare earth element compound of the hydrogen bond type, oligomer type, or a combination thereof and the alkylating agent in step (S10), the catalyst activity can be further improved.

[0089] According to an embodiment of the present invention, step (S20) can be carried out by including a conjugated diene monomer for the same purpose as in step (S10). In this case, if step (S20) is carried out by including a conjugated diene monomer, then step (S20) can be carried out by including the conjugated diene monomer separately or simultaneously with step (S10).

[0090] According to an embodiment of the present invention, if step (S20) is carried out by including a conjugated diene monomer, then relative to 1 mol of the pre-treated lanthanide rare earth element compound of the hydrogen bond type, oligomer type, or a combination thereof in step (S10), more than 1 mol, more than 5 mol, more than 10 mol, more than 15 mol, or more than 20 mol, and 100 mol or less, 90 mol or less, 80 mol or less, 70 mol or less, 60 mol or less, or 50 mol or less of the conjugated diene monomer can be injected.

[0091] According to an embodiment of the present invention, step (S20) can be continuously carried out in a plurality of reactors connected in series. In this case, since alkylation is carried out in a plurality of reactors connected in series, the alkylation can be fully carried out, and the activity of the catalyst composition can be further improved. In this case, the alkylating agent can be injected only into the first reactor of the plurality of reactors connected in series to carry out step (S20), and can be separated and injected into the plurality of reactors connected in series to carry out step (S20). If the alkylating agent is separated and injected into a plurality of reactors, the reactors into which the alkylating agent is injected can be selected as needed. In addition, the types of the alkylating agent separated and injected into the plurality of reactors connected in series can be the same or different from each other.

[0092] According to an embodiment of the present invention, the flow of the reactants in the plurality of reactors connected in series in step (S20) can be independently carried out in a top-down (top injection - bottom removal) manner or a bottom-up (bottom injection - top removal) manner.

[0093] According to an embodiment of the present invention, at least one of the plurality of reactors connected in series in step (S20) can include a tubular reactor provided with a line mixer. In this case, the reactants can remain in the tubular reactor connected between the reactors connected in series, and continuous mixing can be carried out, so that the alkylation can be further fully carried out.

[0094] According to an embodiment of the present invention, step (S30) is a step of halogenating the alkylated lanthanide rare earth element compound in step (S20), which can be carried out by mixing and reacting the alkylated lanthanide rare earth element compound in step (S20) with a halogen compound.

[0095] According to an embodiment of the present invention, the halogen compound can be a diatomic halogen, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, an organometallic halide, etc.

[0096] According to an embodiment of the present invention, the diatomic halogen can include fluorine, chlorine, bromine or iodine.

[0097] According to an embodiment of the present invention, the interhalogen compound can include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, iodine trifluoride, etc.

[0098] According to an embodiment of the present invention, the hydrogen halide can include hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide.

[0099] According to an embodiment of the present invention, the organic halide can include tert-butyl chloride (t-BuCl), tert-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chlorodiphenylmethane, bromodiphenylmethane, trityl chloride, trityl bromide, benzal chloride, benzal bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), 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, trityl iodide, benzal 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, etc.

[0100] According to an embodiment of the present invention, the non-metal halide can include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl 4 )、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.

[0101] According to one embodiment of the present invention, the metal halide may include 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 dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

[0102] According to one embodiment of the present invention, the organometallic halide may be alkylaluminum halide or alkyl sesquialuminum halide. In a specific embodiment, the organometallic halide may include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methyldialuminum chloride, ethyldialuminum chloride, methyldialuminum bromide, ethyldialuminum bromide, methyldialuminum fluoride, ethyldialuminum fluoride, methyl sesquialuminum chloride, ethyl sesquialuminum chloride (EASC), isobutyl sesquialuminum 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, di-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, methyldialuminum iodide, ethyldialuminum iodide, n-butyldialuminum iodide, isobutyldialuminum iodide, methyl sesquialuminum iodide, ethyl sesquialuminum iodide, isobutyl sesquialuminum 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, etc.

[0103] According to one embodiment of the present invention, considering the improvement of catalyst activity and thus reactivity, the halogen compound may be one or more selected from the group consisting of alkylaluminum halide represented by Formula 3 and alkyl sesquialuminum halide represented by Formula 4.

[0104] [Formula 3]

[0105] AlR 7 R 8 R 9

[0106] In Formula 3, R 7 to R 9 may each independently be a halogen group or an alkyl group having 1 to 12 carbon atoms, wherein R 7 to R9 not all of them are halogen groups. In a specific embodiment, in Formula 3, R 7 to R 9 can each independently be a halogen group or an alkyl group having 1 to 6 carbon atoms, wherein not all of R 7 to R 9 are halogen groups. In a more specific embodiment, in Formula 3, R 7 and R 8 can each independently be an alkyl group having 1 to 4 carbon atoms, and R 9 can be a halogen group.

[0107] [Formula 4]

[0108]

[0109] In Formula 4, R 10 to R 12 can each independently be an alkyl group having 1 to 12 carbon atoms, and X 1 to X 3 can each independently be a halogen group. In a specific embodiment, in Formula 4, R 10 to R 12 can each independently be an alkyl group having 1 to 6 carbon atoms. In a more specific embodiment, in Formula 4, R 10 to R 12 can each independently be an alkyl group having 1 to 4 carbon atoms.

[0110] According to an embodiment of the present invention, considering controlling the catalytic reaction and side reactions of the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof in step (S10), the halogen compound can be one or more selected from the group consisting of dialkyl aluminum halide and alkyl aluminum sesquihalide, and the types of dialkyl aluminum halide and alkyl aluminum sesquihalide are the same as those described above. In a specific embodiment, the dialkyl aluminum halide can be diethyl aluminum chloride, and the alkyl aluminum sesquihalide can be ethyl aluminum sesquichloride.

[0111] According to an embodiment of the present invention, step (S30) can be carried out by injecting 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, or injecting 5.0 mol or less, 4.5 mol or less, 4.0 mol or less, 3.5 mol or less, or 3.0 mol or less of the halogen compound relative to 1 mol of the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof in step (S10).

[0112] According to an embodiment of the present invention, step (S30) can be carried out at a temperature above -20°C, above -15°C, or above -10°C and at a temperature below 40°C, below 35°C, below 30°C, below 25°C, or below 20°C.

[0113] According to an embodiment of the present invention, step (S30) can be carried out for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more and for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0114] According to an embodiment of the present invention, by taking into account the molar ratio of the pre-treated lanthanide rare earth element compound of the hydrogen bond type, oligomer type or a combination thereof and the alkylating agent, the reaction temperature and the reaction time in control step (S10), the catalyst activity can be further improved in step (S30).

[0115] According to an embodiment of the present invention, steps (S10) to (S30) can be carried out in an organic solvent. The organic solvent can be a non-polar solvent that is non-reactive with the components of the catalyst composition. In a specific embodiment, the organic solvent can be a straight-chain, branched-chain 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 and methylcyclohexane; a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether, petroleum spirit and kerosene; or an aromatic solvent, such as benzene, toluene, ethylbenzene and xylene. In a more specific embodiment, the organic solvent can be a straight-chain, branched-chain 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 can be used.

[0116] According to an embodiment of the present invention, steps (S10), (S20) and (S30) can each be carried out in a separate reactor connected in series. Therefore, at least three reactors are required to prepare the catalyst according to the preparation method of the catalyst composition. In addition, if step (S20) is continuously carried out in a plurality of reactors connected in series, then one or more reactors for carrying out step (S10), two or more reactors for carrying out step (S20) and one or more reactors for carrying out step (S30) are required to prepare the catalyst according to the preparation method of the catalyst composition, for a total of four or more reactors.

[0117] According to an embodiment of the present invention, steps (S10), (S20), and (S30) can be carried out continuously. That is, steps (S10), (S20), and (S30) can be carried out continuously in separate reactors connected in series, and in this case, the productivity of the catalyst composition and the conjugated diene polymer using the same can be increased, and more uniform quality can be ensured.

[0118] According to an embodiment of the present invention, the flow of the reactants in the separate reactors connected in series can be independently carried out in a top-down manner or a bottom-up manner.

[0119] According to an embodiment of the present invention, all steps of the method for preparing the catalyst composition including steps (S10) to (S30) can be carried out at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher and at a temperature of 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, 20°C or lower, or 15°C or lower.

[0120] According to an embodiment of the present invention, all steps of the method for preparing the catalyst composition including steps (S10) to (S30) can be carried out for 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, or 70 minutes or more and 2 hours or less, 1 hour 50 minutes or less, 1 hour 40 minutes or less, 1 hour 30 minutes or less, 1 hour 20 minutes or less, or 1 hour 10 minutes or less.

[0121] Preparation method of conjugated diene polymer

[0122] The present invention provides a method for preparing a conjugated diene polymer.

[0123] According to an embodiment of the present invention, the method for preparing a conjugated diene polymer may include step (S100) of polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition prepared by the method for preparing the catalyst composition.

[0124] According to an embodiment of the present invention, the conjugated diene monomer that can be injected in step (S100) may be one or more 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, or 2,4-hexadiene.

[0125] According to an embodiment of the present invention, the hydrocarbon solvent in step (S100) may be one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0126] According to an embodiment of the present invention, the catalyst composition may be a catalyst composition prepared by the above-described method for preparing a catalyst composition, and with respect to a total of 100 g of the conjugated diene monomer, the catalyst composition may be used in an amount of 0.03 mmol or more, 0.04 mmol or more, 0.05 mmol or more, or 0.06 mmol or more and in an amount of 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 of the neodymium compound.

[0127] According to an embodiment of the present invention, the polymerization in step (S100) may be carried out by continuous polymerization in a polymerization reactor including at least two reactors or in a batch reactor. Additionally, the polymerization may be heat polymerization, isothermal polymerization, or isothermal polymerization (adiabatic polymerization).

[0128] According to an embodiment of the present invention, isothermal polymerization may refer to polymerization that uses the heat of the self-reaction without arbitrarily applying heat after injecting the catalyst composition, and heat polymerization may refer to injecting the catalyst composition and then raising the temperature by arbitrarily applying heat. Isothermal polymerization may refer to adding or removing heat by applying heat after adding the catalyst composition to keep the temperature of the reactants constant.

[0129] According to an embodiment of the present invention, the polymerization in step (S100) may be carried out by coordination anionic polymerization, and the polymerization environment may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, specifically solution polymerization.

[0130] According to an embodiment of the present invention, the polymerization in step (S100) may 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 200°C or lower, 150°C or lower, 120°C or lower, or 90°C or lower. Within this range, the polymerization reaction can be smoothly controlled, and the cis-1,4 bond content of the conjugated diene polymer produced thereby can be ensured.

[0131] According to an 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 not more than 3 hours, not more than 2 hours and 30 minutes, or not more than 2 hours.

[0132] According to an embodiment of the present invention, the conjugated diene polymer formed by the polymerization in step (S100) can be an active polymer containing a portion activated by the catalyst composition.

[0133] According to an embodiment of the present invention, step (S200) of reacting the active polymer with a modifier may be included. The modifier can be a known modifier that can be used in the process of preparing a conjugated diene polymer using a catalyst composition containing a lanthanide rare earth element compound.

[0134] According to an embodiment of the present invention, the method for preparing a conjugated diene polymer may include, after preparing the active polymer, a step of completing the polymerization by further using additives such as polyethylene glycol phosphate, a reaction quencher for completing the polymerization reaction, and antioxidants such as 2,6 - di - tert - butyl - p - cresol. Additionally, additives commonly used to promote solution polymerization, such as chelating agents, dispersants, pH control agents, deoxidizers, and oxygen scavengers, etc., may be selectively further used together with the reaction quencher.

[0135] Conjugated diene polymer

[0136] The present invention provides a conjugated diene polymer.

[0137] According to an embodiment of the present invention, the conjugated diene polymer can be prepared by the method for preparing a conjugated diene polymer. That is, the conjugated diene polymer can be polymerized in the presence of a catalyst composition prepared by the method for preparing the above - mentioned catalyst composition.

[0138] According to an embodiment of the present invention, the conjugated diene polymer may include conjugated diene monomer units. The conjugated diene monomer units refer to repeating units formed by polymerizing conjugated diene monomers.

[0139] According to an embodiment of the present invention, the conjugated diene polymer may contain 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight of 1,3-butadiene monomer units, and optionally, 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less of other conjugated diene monomers copolymerizable with 1,3-butadiene. Within this range, the effect of preventing a decrease in the 1,4-cis bond content in the conjugated diene polymer can be achieved. The 1,3-butadiene monomer may be 1,3-butadiene or its derivatives, including 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-ethyl-1,3-butadiene. As other conjugated diene monomers copolymerizable with 1,3-butadiene, 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 may be used.

[0140] According to an embodiment of the present invention, the conjugated diene polymer may be a conjugated diene polymer catalyzed by a catalyst composition containing a lanthanide 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 containing a neodymium compound.

[0141] According to an embodiment of the present invention, the weight average molecular weight (Mw) of the conjugated diene polymer may be 1.0×10 5 g / mol or more, 2.0×10 5 g / mol or more, 3.0×10 5 g / mol or more, 4.0×10 5 g / mol or more, 5.0×10 5 g / mol or more, 6.0×10 5 g / mol or more, 7.0×10 5 g / mol or more, 8.0×10 5 g / mol or more, or 9.0×10 5 g / mol or more and 1.0×10 6 g / mol or less, 9.0×10 5 g / mol or less, 8.0×10 5 g / mol or less, 7.0×10 5 g / mol or less, 6.0×10 5 g / mol or less, 5.0×10 5 g / mol or less, 4.0×10 5 g / mol or less, or 3.0×10 5less than g / mol. Additionally, the number-average molecular weight (Mn) of the conjugated diene polymer can be 1.0×10 5 g / mol or more, 2.0×10 5 g / mol or more, 3.0×10 5 g / mol or more, 4.0×10 5 g / mol or more, or 5.0×10 5 g / mol or more and 6.0×10 5 g / mol or less, 5.0×10 5 g / mol or less, 4.0×10 5 g / mol or less, 3.0×10 5 g / mol or less, 2.0×10 5 g / mol or less, or 1.0×10 5 g / mol or less. Within this range, when applied to a rubber composition, the tensile properties are excellent, the processability is excellent, and the workability of the rubber composition is improved for easy mixing and kneading. Therefore, excellent effects of balancing the mechanical properties and physical properties of the rubber composition can be achieved.

[0142] According to one embodiment of the present invention, the molecular weight distribution (Mw / Mn) of the conjugated diene polymer can be 1.0 or more, 1.5 or more, 2.0 or more, 2.1 or more, 2.2 or more, or 2.3 or more and 4.0 or less, 3.5 or less, 3.0 or less, or 2.5 or less. The molecular weight distribution can be calculated from the ratio (Mw / Mn) of the weight-average molecular weight (Mw) and the number-average molecular weight (Mn). In this case, the number-average molecular weight (Mn) is the common average of the individual polymer molecular weights obtained by measuring the molecular weights of n polymer chains, obtaining the sum of the molecular weights, and dividing the sum by n, and the weight-average molecular weight (Mw) represents the polydispersity of the polymer composition. Additionally, each of the weight-average molecular weight and the number-average molecular weight can refer to the polystyrene-equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0143] According to an embodiment of the present invention, if the conjugated diene polymer simultaneously satisfies the weight-average molecular weight (Mn) and number-average molecular weight conditions and the molecular weight distribution, and if applied to a rubber composition, the tensile properties, viscoelasticity, and processability of the rubber composition can be excellent, and excellent effects of balancing the physical properties can be achieved.

[0144] According to an embodiment of the present invention, the content of cis-1,4 bonds in the conjugated diene polymer can be 97.0% by weight or more, 97.1% by weight or more, 97.2% by weight or more, 97.3% by weight or more, 97.4% by weight or more, 97.5% by weight or more, 97.6% by weight or more, 97.7% by weight or more, 97.8% by weight or more, 97.9% by weight or more, 98.0% by weight or more, or 98.1% by weight or more and 100.0% by weight or less, 99.5% by weight or less, or 99.0% by weight or less.

[0145] According to an embodiment of the present invention, the Mooney viscosity (ML1+4, @100 °C) of the conjugated diene polymer can be 30 or more, 35 or more, 40 or more, 41 or more, 42 or more, 43 or more, 44 or more, or 45 or more and 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, or 49 or less.

[0146] Rubber composition

[0147] The present invention provides a rubber composition.

[0148] According to an embodiment of the present invention, the rubber composition may contain a conjugated diene polymer. In a specific embodiment, the rubber composition may contain a 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 100% by weight or less, 95% by weight or less, or 90% by weight or less. Within this range, the abrasion resistance and crack resistance of molded articles such as tires made using the rubber composition can be sufficiently ensured.

[0149] According to an embodiment of the present invention, if necessary, in addition to the conjugated diene polymer, the rubber composition may further contain other rubber components. In this case, the content of the rubber component may be 90% by weight or less relative to the total weight of the rubber composition. Specifically, the content of the rubber component may be 1 part by weight to 900 parts by weight relative to 100 parts by weight of the conjugated diene copolymer.

[0150] According to an embodiment of the present invention, the rubber component may be natural rubber or synthetic rubber. For example, it includes natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubber obtained by modifying or refining general natural rubber, such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber; and synthetic rubbers, 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, acrolein-based rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, and halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

[0151] According to an embodiment of the present invention, relative to 100 parts by weight of the conjugated diene polymer, the rubber composition may contain 20 to 90 parts by weight of a filler, and the filler may be a silica-based filler, a carbon black-based filler, or a combination thereof. Specifically, the filler may be a carbon black-based filler.

[0152] According to an embodiment of the present invention, the nitrogen adsorption specific surface area of the carbon black-based filler may be 20 m 2 / g to 250 m 2 / g (measured based on N2SA, JIS K 6217-2:2001). Within this range, the processability of the rubber composition may be excellent, and the reinforcing performance of the filler can be sufficiently ensured. Additionally, the dibutyl phthalate oil absorption (DBP) of the carbon black-based filler may be 80 cc / 100 g to 200 cc / 100 g. Within this range, the processability of the rubber composition may be excellent, and the reinforcing performance of the filler can be sufficiently ensured.

[0153] According to an embodiment of the present invention, the silica-based filler may include wet silica (hydrated silica), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica-based filler may be wet silica, which has the most significant compatibility effect between the improvement effect of the destruction characteristics and the wet grip. Additionally, the silica-based filler may have a nitrogen adsorption specific surface area of 120 m 2 / g to 180 m 2 / g, a nitrogen surface area per gram (N2SA), of 100 m 2 / g to 200 m 2The adsorption specific surface area of cetyltrimethylammonium bromide (CTAB) per g. Within this range, the processability of the rubber composition can be excellent, and the reinforcing performance of the filler can be sufficiently ensured.

[0154] According to one embodiment of the present invention, if a silica-based filler is used as the filler, a silane coupling agent can be used together to improve the reinforcing performance and low heat release performance. The silane coupling agent can include 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-dimethylthiocarbamyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyl dimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. In a specific embodiment, considering the improvement effect of the reinforcing performance, the silane coupling agent can be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazolyltetrasulfide.

[0155] According to one embodiment of the present invention, the rubber composition can be sulfur-crosslinkable, and thus a vulcanizing agent can be further included. The vulcanizing agent can specifically be sulfur powder, and the content can be 0.1 parts by weight to 10 parts by weight relative to 100 parts by weight of the rubber component. Within this range, the required elasticity and strength of the vulcanized rubber composition can be ensured, and at the same time, a low fuel consumption rate can be obtained.

[0156] According to one embodiment of the present invention, in addition to the above components, the rubber composition can further include various additives used in the general rubber industry, specifically, vulcanization accelerators, processing oils, plasticizers, anti-aging agents, scorch inhibitors, zinc white, stearic acid, thermosetting resins, or thermoplastic resins, etc.

[0157] According to an embodiment of the present invention, the vulcanization accelerator is not particularly limited and may specifically include thiazole compounds such as 2-mercaptobenzothiazole (M), dibenzothiazole disulfide (DM), and N-cyclohexyl-2-benzothiazolyl sulfenamide (CZ), or guanidine compounds such as diphenylguanidine (DPG). The content of the vulcanization accelerator may be from 0.1 parts by weight to 5 parts by weight relative to 100 parts by weight of the rubber component.

[0158] According to an embodiment of the present invention, the processing oil acts as a softening agent in the rubber composition and may specifically include paraffin-based, naphthenic, or aromatic compounds. More specifically, considering the tensile strength and abrasion resistance, aromatic processing oils can be used, and considering the hysteresis loss and performance at low temperatures, naphthenic or paraffin-based processing oils can be used. The content of the processing oil may be 100 parts by weight or less relative to 100 parts by weight of the rubber component. Within this range, deterioration of the tensile strength and low heat generation performance (low fuel consumption rate) of the vulcanized rubber can be prevented.

[0159] According to an embodiment of the present invention, the anti-aging agent may include 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 condensate of diphenylamine and acetone at high temperature. The usage amount of the anti-aging agent may be from 0.1 parts by weight to 6 parts by weight relative to 100 parts by weight of the rubber component.

[0160] According to an embodiment of the present invention, the rubber composition can be obtained by kneading using kneading equipment such as a Banbury mixer, rolls, and an internal mixer according to a mixing formula. Additionally, a rubber composition having low heat generation performance and excellent abrasion resistance can be obtained through a vulcanization process after a molding process.

[0161] According to an embodiment of the present invention, the rubber composition can be used to manufacture various components of a tire, such as a tire tread, a base tread, a sidewall, a carcass coating rubber, a belt layer coating rubber, a bead filler, a bead wrapper, and a bead coating rubber, or to manufacture rubber products in various industries, such as anti-vibration rubber, a belt conveyor, and a hose. In a specific embodiment, the molded article manufactured using the rubber composition may include a tire or a tire tread.

[0162] Hereinafter, embodiments of the present invention will be explained in detail so that those skilled in the art can easily carry them out. However, the embodiments of the present invention can be modified in various other types and should not be limited to the embodiments described below.

[0163] Examples

[0164] Example 1

[0165] Three pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.16 kg / hr, and at the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.05 kg / hr, and a trioctylaluminum solution diluted to a concentration of 25 wt% in n-hexane is continuously injected in an amount such that trioctylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C, and after continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and into the second reactor, a diisobutylaluminum hydride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C, and after continuous injection for 30 minutes, the reactants in the second reactor are transferred to the third reactor, and into the third reactor, a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected in an amount such that diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C, and after continuous injection for 30 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0166] Example 2

[0167] Three pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.16 kg / hr. And simultaneously, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.05 kg / hr, and a trioctylaluminum solution diluted to a concentration of 25 wt% in n-hexane is continuously injected in an amount such that trioctylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10°C. And after continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and into the second reactor, a triisobutylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that triisobutylaluminum is 30 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10°C. And after continuous injection for 30 minutes, the reactants in the second reactor are transferred to the third reactor, and into the third reactor, a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected in an amount such that diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5°C. And after continuous injection for 30 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0°C.

[0168] Example 3

[0169] Three pressure-resistant reactors with a capacity of 300 ml, equipped with jackets and stirrers, are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.12 kg / hr. At the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.03 kg / hr, and a trioctylaluminum solution diluted to a concentration of 25 wt% in n-hexane is continuously injected in an amount such that the amount of trioctylaluminum is 20 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C. After continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and a diisobutylaluminum hydride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected into the second reactor in an amount such that the amount of diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C. After continuous injection for 30 minutes, the reactants in the second reactor are transferred to the third reactor, and a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected into the third reactor in an amount such that the amount of diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C. After continuous injection for 30 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0170] Example 4

[0171] Three pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.16 kg / hr. And at the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.05 kg / hr, and a tri-n-octylaluminum solution diluted to a concentration of 25 wt% in n-hexane is continuously injected in an amount such that tri-n-octylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C, and after continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and a diisobutylaluminum hydride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected into the second reactor in an amount such that diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C, and after continuous injection for 30 minutes, the reactants in the second reactor are transferred to the third reactor, and an ethyl sesquichloride solution diluted to a concentration of 10 wt% in n-hexane is continuously injected into the third reactor in an amount such that ethyl sesquichloride is 1.5 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C, and after continuous injection for 30 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0172] Example 5

[0173] Three pressure-resistant reactors with a capacity of 300 ml, equipped with jackets and stirrers, are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.16 kg / hr. And simultaneously, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.05 kg / hr, and a tri-n-octylaluminum solution diluted to a concentration of 25 wt% in n-hexane is continuously injected in an amount such that the tri-n-octylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C, and after 30 minutes of continuous injection, the mixture mixed in the first reactor is transferred to the second reactor, and into the second reactor, a diisobutylaluminum hydride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that the diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 20 °C, and after 30 minutes of continuous injection, the reactants in the second reactor are transferred to the third reactor, and into the third reactor, a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected in an amount such that the diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C, and after 30 minutes of continuous injection, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0174] Example 6

[0175] Four pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 15 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.08 kg / hr. And simultaneously, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.07 kg / hr, and a trioctylaluminum solution diluted to a concentration of 25 wt% in n-hexane is continuously injected in an amount of 10 mol of trioctylaluminum per 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C. And after continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and into the second reactor, a diisobutylaluminum hydride solution diluted to a concentration of 10 wt% in n-hexane is continuously injected in an amount of 15 mol of diisobutylaluminum hydride per 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C. And after continuous injection for 15 minutes, the reactants in the second reactor are transferred to the third reactor. The third reactor is operated at a temperature of 10 °C. And after continuous injection for 15 minutes, the reactants in the third reactor are transferred to the fourth reactor. Into the fourth reactor, a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected in an amount of 3 mol of diethylaluminum chloride per 1 mol of neodymium. The fourth reactor is operated at a temperature of -5 °C. And after continuous injection for 15 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0176] Example 7

[0177] Four pressure-resistant reactors with a capacity of 300 ml, equipped with jackets and stirrers, are connected in series and used as continuous catalyst production reactors. In this case, a pipeline equipped with a line mixer is used to connect the third reactor and the fourth reactor. Each reactor is maintained in a nitrogen atmosphere. A solution of neodymium versatate diluted to a concentration of 15 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.08 kg / hr. At the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.07 kg / hr, and a solution of trioctylaluminum diluted to a concentration of 25 wt% in n-hexane is continuously injected in an amount of 10 mol of trioctylaluminum relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10°C. After 30 minutes of continuous injection, the mixture mixed in the first reactor is transferred to the second reactor, and a solution of diisobutylaluminum hydride diluted to a concentration of 10 wt% in n-hexane is continuously injected into the second reactor in an amount of 15 mol of diisobutylaluminum hydride relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10°C. After 15 minutes of continuous injection, the reactants in the second reactor are transferred to the third reactor. The third reactor is operated at a temperature of 10°C. After 15 minutes of continuous injection, the reactants in the third reactor are left in the pipeline equipped with a line mixer at a temperature of 0°C for 15 minutes and then transferred to the fourth reactor. A solution of diethylaluminum chloride diluted to a concentration of 30 wt% in n-hexane is continuously injected into the fourth reactor in an amount of 3 mol of diethylaluminum chloride relative to 1 mol of neodymium. The fourth reactor is operated at a temperature of -5°C. After 15 minutes of continuous injection, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0°C.

[0178] Example 8

[0179] Three pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.24 kg / hr, and at the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-hexylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount of 10 mol of tri-n-hexylaluminum per 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C, and after 30 minutes of continuous injection, the mixture mixed in the first reactor is transferred to the second reactor, and a solution of diisobutylaluminum hydride diluted to a concentration of 50 wt% in n-hexane is continuously injected into the second reactor in an amount of 15 mol of diisobutylaluminum hydride per 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C, and after 30 minutes of continuous injection, the reactants in the second reactor are transferred to the third reactor, and a solution of diethylaluminum chloride diluted to a concentration of 30 wt% in n-hexane is continuously injected into the third reactor in an amount of 3 mol of diethylaluminum chloride per 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C, and after 30 minutes of continuous injection, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0180] Example 9

[0181] Three pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.20 kg / hr. And at the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.06 kg / hr, and a tri-n-hexylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that tri-n-hexylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C. And after continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and into the second reactor, a tri-isobutylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that tri-isobutylaluminum is 30 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C. And after continuous injection for 30 minutes, the reactants in the second reactor are transferred to the third reactor, and into the third reactor, a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected in an amount such that diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C. And after continuous injection for 30 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0182] Example 10

[0183] Three pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.20 kg / hr. And simultaneously, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.06 kg / hr, and a tri-n-hexylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount of 20 mol of tri-n-hexylaluminum per 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C. And after 30 minutes of continuous injection, the mixture mixed in the first reactor is transferred to the second reactor, and into the second reactor, a diisobutylaluminum hydride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount of 15 mol of diisobutylaluminum hydride per 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C. And after 30 minutes of continuous injection, the reactants in the second reactor are transferred to the third reactor, and into the third reactor, a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected in an amount of 3 mol of diethylaluminum chloride per 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C. And after 30 minutes of continuous injection, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0184] Example 11

[0185] Three pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.24 kg / hr, and at the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-hexylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that tri-n-hexylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C, and after continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and a diisobutylaluminum hydride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected into the second reactor in an amount such that diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C, and after continuous injection for 30 minutes, the reactants in the second reactor are transferred to the third reactor, and an ethyl sesquichloride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected into the third reactor in an amount such that ethyl sesquichloride is 1.5 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C, and after continuous injection for 30 minutes, a portion of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0186] Example 12

[0187] Three pressure-resistant reactors with a capacity of 300 ml, equipped with jackets and stirrers, are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.24 kg / hr. And simultaneously, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-hexylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that tri-n-hexylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C, and after 30 minutes of continuous injection, the mixture mixed in the first reactor is transferred to the second reactor, and a diisobutylaluminum hydride solution diluted to a concentration of 50 wt% in n-hexane is continuously injected into the second reactor in an amount such that diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 20 °C, and after 30 minutes of continuous injection, the reactants in the second reactor are transferred to the third reactor, and a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected into the third reactor in an amount such that diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The third reactor is operated at a temperature of -5 °C, and after 30 minutes of continuous injection, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0188] Example 13

[0189] Four pressure-resistant reactors with a capacity of 300 ml, equipped with jackets and stirrers, are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 10 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.14 kg / hr. And simultaneously, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.08 kg / hr, and a tri-n-hexylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that the tri-n-hexylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10 °C, and after 30 minutes of continuous injection, the mixture mixed in the first reactor is transferred to the second reactor, and into the second reactor, a diisobutylaluminum hydride solution diluted to a concentration of 10 wt% in n-hexane is continuously injected in an amount such that the diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10 °C, and after 15 minutes of continuous injection, the reactants in the second reactor are transferred to the third reactor. The third reactor is operated at a temperature of 10 °C, and after 15 minutes of continuous injection, the reactants in the third reactor are transferred to the fourth reactor. Into the fourth reactor, a diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected in an amount such that the diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The fourth reactor is operated at a temperature of -5 °C, and after 15 minutes of continuous injection, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0190] Example 14

[0191] Four pressure-resistant reactors with a capacity of 300 ml, equipped with jackets and stirrers, are connected in series and used as continuous catalyst production reactors. In this case, a pipeline equipped with a line mixer is used to connect the third reactor and the fourth reactor. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 10 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.14 kg / hr. At the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.08 kg / hr, and a tri-n-hexylaluminum solution diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that the amount of tri-n-hexylaluminum is 10 mol relative to 1 mol of neodymium. The first reactor is operated at a temperature of 10°C. After continuous injection for 30 minutes, the mixture mixed in the first reactor is transferred to the second reactor, and a diisobutylaluminum hydride solution diluted to a concentration of 10 wt% in n-hexane is continuously injected into the second reactor in an amount such that the amount of diisobutylaluminum hydride is 15 mol relative to 1 mol of neodymium. The second reactor is operated at a temperature of 10°C. After continuous injection for 15 minutes, the reactants in the second reactor are transferred to the third reactor. The third reactor is operated at a temperature of 0°C. After continuous injection for 15 minutes, the reactants in the third reactor are left in the pipeline equipped with a line mixer at a temperature of 0°C for 15 minutes and then transferred to the fourth reactor. A diethylaluminum chloride solution diluted to a concentration of 30 wt% in n-hexane is continuously injected into the fourth reactor in an amount such that the amount of diethylaluminum chloride is 3 mol relative to 1 mol of neodymium. The fourth reactor is operated at a temperature of -5°C. After continuous injection for 15 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0°C.

[0192] Comparative Example 1

[0193] Two pressure-resistant reactors with a capacity of 300 ml equipped with jackets and stirrers are connected in series and used as continuous catalyst production reactors. Each reactor is maintained under a nitrogen atmosphere. A neodymium versatate solution diluted to a concentration of 5 wt% in n-hexane is continuously injected into the first reactor at a flow rate of 0.32 kg / hr, and at the same time, 1,3-butadiene diluted to a concentration of 5 wt% in n-hexane is continuously injected at a flow rate of 0.09 kg / hr, and a solution of diisobutylaluminum hydride diluted to a concentration of 50 wt% in n-hexane is continuously injected in an amount such that the amount of diisobutylaluminum hydride relative to 1 mol of neodymium is 15 mol. The first reactor is operated at a temperature of 10 °C, and after continuous injection for 30 minutes, the reactants in the first reactor are transferred to the second reactor, and a solution of diethylaluminum chloride diluted to a concentration of 30 wt% in n-hexane is continuously injected into the second reactor in an amount such that the amount of diethylaluminum chloride relative to 1 mol of neodymium is 3 mol. The second reactor is operated at a temperature of -5 °C, and after continuous injection for 30 minutes, a part of the catalyst composition prepared in the pressure-resistant reactor under a nitrogen atmosphere is taken out and stored at a temperature below 0 °C.

[0194] Comparative Example 2

[0195] 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane and 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n-hexane were injected into the reactor. Then, at a temperature of 10 °C, diisobutylaluminum hydride was injected into the reactor in an amount such that the amount of diisobutylaluminum hydride relative to 1 mol of neodymium was 15 mol, and then stirred for 30 minutes. Then, at a temperature of -5 °C, diethylaluminum chloride was injected into the reactor in an amount such that the amount of diethylaluminum chloride relative to 1 mol of neodymium was 3 mol, and then stirred for 30 minutes to prepare a catalyst composition.

[0196] Comparative Example 3

[0197] 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane and 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n-hexane were injected into the reactor. Then, at a temperature of 10 °C, triisobutylaluminum was injected into the reactor in an amount such that the amount of triisobutylaluminum relative to 1 mol of neodymium was 30 mol, and then stirred for 30 minutes. Then, at a temperature of -5 °C, diethylaluminum chloride was injected into the reactor in an amount such that the amount of diethylaluminum chloride relative to 1 mol of neodymium was 3 mol, and then stirred for 30 minutes to prepare a catalyst composition.

[0198] Experimental Example

[0199] Experimental Example 1: Preparation of Conjugated Diene Polymer and Evaluation of Catalyst Composition Activity

[0200] 500 g of 1,3-butadiene and 4.2 kg of n-hexane were injected into a 20 L autoclave reactor, and the internal temperature of the reactor was raised to 70 °C. If the catalyst compositions prepared in Examples 1 to 14 were used, 0.02 parts by weight of diisobutylaluminum hydride was added to the reactor as a molecular weight regulator relative to 100 parts by weight of 1,3-butadiene, or if the catalyst compositions prepared in Comparative Examples 1 to 3 were used, 0.05 parts by weight of diisobutylaluminum hydride was added to the reactor as a molecular weight regulator relative to 100 parts by weight of 1,3-butadiene. Then, each catalyst composition prepared in Examples 1 to 14 and Comparative Examples 1 to 3 was injected, and then polymerization was carried out. At the time point when the polymerization conversion rate reached 98% or more, a n-hexane solution containing 1.0 g of a polymerization inhibitor and a n-hexane solution in which 30 wt% of Irganox 1520 antioxidant (BASF) was dissolved were added to quench the reaction, and the polymer thus obtained was put into hot water heated by steam and stirred to remove the solvent. The resulting product was roll-dried to remove the remaining solvent and water, thereby preparing a butadiene polymer.

[0201] In the process of preparing the butadiene polymer, 25 minutes after the start of the reaction from the polymerization starting point, a part of the polymerization solution was taken, the total solid content (TSC, %) was measured, and the polymerization conversion rate was calculated according to the following Equation 1. For each catalyst composition of Examples 1 to 14 and Comparative Examples 1 to 3, the polymerization conversion rate 25 minutes after the start of the reaction was measured, and the activities of the catalyst compositions were evaluated and shown in Tables 1 to 3. Based on the measured value of Comparative Example 2 as a reference value, the activities of the catalyst compositions of the Examples and Comparative Examples were indexed using Equation 2.

[0202] [Equation 1]

[0203] Polymerization conversion rate (%) = TSC (%) of the sample / Concentration (wt%) of the injected 1,3-butadiene

[0204] [Equation 2]

[0205] Activity index = (Measured value / Reference value) × 100

[0206] [Table 1]

[0207]

[0208] [Table 2]

[0209]

[0210] [Table 3]

[0211] Classification Comparative Example 1 Comparative Example 2 Comparative Example 3 Activity (polymerization conversion rate at 25 minutes, %) 54 55 45 Activity index (%) 98 100 82

[0212] As shown in Table 1, it was confirmed that the catalyst compositions prepared in Examples 1 to 14 showed very high activity of the catalyst compositions as compared with Comparative Examples 1 to 3.

[0213] In contrast, in Comparative Example 1 where the lanthanide rare earth element compound was not pretreated with tri-n-hexylaluminum and tri-n-octylaluminum according to the present invention, it was confirmed that the activity of the catalyst composition was reduced as compared with Examples 1 to 14, particularly Examples 1, 3 to 8, and 10 to 14 using the same alkylating agent and halogen compound.

[0214] In addition, in Comparative Example 2 where the lanthanide rare earth element compound was not pretreated with tri-n-hexylaluminum and tri-n-octylaluminum according to the present invention but was prepared using a rotary evaporator, it was confirmed that the activity of the catalyst composition was reduced as compared with Examples 1 to 14, particularly Examples 1, 3 to 8, and 10 to 14 using the same alkylating agent and halogen compound.

[0215] In addition, in Comparative Example 3 where the lanthanide rare earth element compound was not pretreated with tri-n-hexylaluminum and tri-n-octylaluminum according to the present invention but was prepared using a rotary evaporator, it was confirmed that although the alkylating agent was changed to triisobutylaluminum and used in excess, alkylation could not be sufficiently carried out, and thus the activity of the catalyst composition was reduced as compared with Examples 1 to 14, particularly Examples 2 and 9 using the same alkylating agent and halogen compound.

[0216] Experimental Example 2: Evaluation of Physical Properties of Conjugated Diene Polymers

[0217] For the conjugated diene polymers prepared using the catalyst compositions of Examples 1 to 14 and Comparative Examples 1 to 3 in Experimental Example 1, the Mooney viscosity, molecular weight distribution, and cis-1,4 bond content were measured and shown in Tables 4 to 6 below.

[0218] * Mooney viscosity (ML1+4, @100 °C): For each polymer, the Mooney viscosity was measured at 100 °C with a rotor speed of 2 ± 0.02 rpm using a large rotor of MV2000E from Monsanto. In this case, the sample used was allowed to stand at room temperature (23 ± 3 °C) for more than 30 minutes, 27 ± 3 g of the sample was taken and placed in the mold cavity, and the measurement was carried out while applying torque by operating the platen.

[0219] *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, and flowed on a gel permeation chromatography (GPC). In this case, two PLgel Olexis columns (product name) of Polymer laboratories and one PLgel mixed-C column were used in combination. Additionally, the newly replaced columns were all mixed-bed type columns, and polystyrene was used as the GPC standard material.

[0220] *Cis-1,4 bond content: The cis-1,4 bond content of the conjugated diene portion was measured by Fourier transform infrared spectroscopy (FT-IR). Specifically, using carbon disulfide in the same cell as the blank, the FT-IR transmission spectrum of a carbon disulfide solution of the conjugated diene polymer prepared at a concentration of 5 mg / mL was measured, and the maximum peak (a, baseline) at approximately 1130 cm -1 was used to show the minimum peak (b) at approximately 967 cm of the trans-1,4 bond, the minimum peak (c) at approximately 911 cm to show the vinyl bond, and the minimum peak (d) at approximately 736 cm to show the cis-1,4 bond to obtain each content. -1 of the trans-1,4 bond, the minimum peak (c) at approximately 911 cm -1 to show the vinyl bond, and the minimum peak (d) at approximately 736 cm -1 to show the cis-1,4 bond to obtain each content.

[0221] [Table 4]

[0222]

[0223] [Table 5]

[0224]

[0225] [Table 6]

[0226] Classification Comparative Example 1 Comparative Example 2 Comparative Example 3 Mooney viscosity (MU) 43 45 48 Molecular weight distribution 2.9 2.9 3.1 Content of cis-1,4 bond (wt%) 97.6 97.5 97.1

[0227] As shown in Tables 4 to 6, it was confirmed that the conjugated diene polymers prepared using the catalyst compositions prepared in Examples 1 to 14 showed appropriate levels of Mooney viscosity and molecular weight distribution while ensuring a high level of cis-1,4 bond content.

[0228] In contrast, compared with Examples 1 to 14, the conjugated diene polymers prepared using the catalyst compositions prepared in Comparative Examples 1 to 3 showed a broad molecular weight distribution.

[0229] Experimental Example 3: Evaluation of Physical Properties of Rubber Composition

[0230] Using the conjugated diene polymers prepared with the catalyst compositions of Examples 1 to 14 and Comparative Examples 1 to 3 in Experimental Example 1, rubber compositions and rubber specimens were prepared, and the Mooney viscosity, abrasion resistance, tensile properties, and viscoelastic properties were measured by the following methods and shown in Tables 7 to 9 below.

[0231] <Preparation of Rubber Compositions and Rubber Specimens>

[0232] For each 100 parts by weight of the conjugated diene polymer prepared with the catalyst compositions of Examples 1 to 14 and Comparative Examples 1 to 3 in Experimental Example 1, 70 parts by weight of carbon black, 22.5 parts by weight of processing oil (TDAE oil), 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO), and 2 parts by weight of stearic acid were mixed.

[0233] Then, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), and 0.5 part by weight of vulcanization accelerator (DPG) were added to each rubber composition, and the resulting mixture was gently mixed at 50 °C at 50 rpm for 1 minute and 30 seconds, and a sheet-like vulcanization blend was formed using a roll at 50 °C. The vulcanization blend was vulcanized at 160 °C for 25 minutes to form a rubber specimen.

[0234] * Tensile properties: Each of the prepared rubber compositions was vulcanized at 150 °C for t90 minutes, and then based on ASTM D412, the modulus (M-300%, kg·f / cm 2 ) when the vulcanizate was elongated by 300% was measured. Based on the measured value of Comparative Example 2 as a reference value, the 300% modulus of the examples and comparative examples was indexed using Equation 3.

[0235] [Equation 3]

[0236] M-300% index = (measured value / reference value) × 100

[0237] * Viscoelastic properties: The viscoelastic property coefficient (tanδ) at -60 °C to 60 °C was measured using a DMTS 500N from GABO GmbH (Germany) at a frequency of 10 Hz, a prestrain of 3%, and a dynamic strain of 3%. In this case, the tanδ value at 0 °C represents the anti-slip resistance, and the tanδ value at 60 °C represents the rolling resistance (fuel consumption rate). Based on the measured value of Comparative Example 2 as a reference value, the viscoelastic properties of the examples and comparative examples were indexed using Equation 4.

[0238] [Equation 4]

[0239] Tanδ60 °C index = (reference value / measured value) × 100

[0240] *Abrasion resistance: The DIN wear test was performed on each formed rubber specimen based on ASTM D5963 and is shown as the DIN weight loss index (loss volume index: abrasion resistance index (ARIA, Method A)). Based on the measured value of Comparative Example 2 as a reference value, the abrasion resistance of the examples and comparative examples was indexed using Equation 5.

[0241] [Equation 5]

[0242] Abrasion amount index = (reference value / measured value) × 100

[0243] [Table 7]

[0244]

[0245] [Table 8]

[0246]

[0247] [Table 9]

[0248]

[0249] As shown in Tables 7 to 9, it can be confirmed that the rubber compositions prepared by including conjugated diene polymers prepared using the catalyst compositions prepared in Examples 1 to 14 show improved tensile properties, viscoelastic properties, and abrasion resistance compared to the rubber compositions prepared by including conjugated diene polymers prepared using the catalyst compositions prepared in Comparative Examples 1 to 3.

[0250] On the contrary, it can be confirmed that the rubber compositions prepared by including conjugated diene polymers prepared using the catalyst compositions prepared in Comparative Examples 1 and 3 show deteriorated tensile properties, viscoelastic properties, and abrasion resistance compared to the rubber compositions prepared by including conjugated diene polymers prepared using the catalyst composition prepared in Comparative Example 2.

[0251] This result was obtained because: during the preparation of the catalyst composition for preparing the conjugated diene polymer, the catalyst activity was improved by pretreating the hydrogen bond type lanthanide rare earth element compound and / or oligomer type lanthanide rare earth element compound that cause deterioration of the catalyst activity before alkylation.

[0252] From the above results, it can be confirmed that the catalyst composition prepared by the method for preparing the catalyst composition according to the present invention shows excellent catalyst activity by pretreating the hydrogen bond type lanthanide rare earth element compound and / or oligomer type lanthanide rare earth element compound that cause deterioration of the catalyst activity before alkylation.

[0253] In addition, it can be confirmed that the conjugated diene polymer prepared by the method for preparing a conjugated diene polymer according to the present invention has a small content of lanthanide rare earth elements remaining in the conjugated diene polymer due to high catalyst activity, a high content of cis bonds and linearity, a narrow molecular weight distribution, and when applied to a rubber composition, exhibits excellent abrasion resistance and low fuel consumption.

Claims

1. A method for preparing a catalyst composition, the method comprising: A step (S10) of performing a pretreatment reaction of a hydrogen bonding type, an oligomer type or a combination thereof on the lanthanide rare earth element compound; an alkylation step (S20) of mixing and reacting the hydrogen bond type, oligomer type or combination thereof pretreated lanthanide rare earth element compound in the step (S10) with an alkylating agent; as well as a halogenation step (S30) of mixing and reacting the alkylated lanthanide rare earth element compound in the step (S20) with a halogen compound, The step (S10) is carried out by mixing and reacting the lanthanide rare earth element compound with one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, and The step (S10), the step (S20), and the step (S30) are each performed in separate reactors connected in series.

2. The method for preparing the catalyst composition according to claim 1, wherein: The step (S10) is performed before the lanthanide rare earth element compound is alkylated by the trialkylaluminum.

3. The method for preparing the catalyst composition according to claim 1, wherein: The lanthanide rare earth element compound is a neodymium compound represented by the following formula 1: [Formula 1] In formula 1, R 1 To R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein R 1 To R 3 Not all hydrogen.

4. The method for preparing the catalyst composition according to claim 1, wherein: The lanthanide rare earth element compound is selected from Nd(2-ethylhexanoic acid)3, Nd(2,2-dimethyldecanoic acid)3, Nd(2,2-diethyldecanoic acid)3, Nd(2,2-dipropyldecanoic acid)3, Nd(2,2-dibutyldecanoic acid)3, Nd(2,2-dihexyldecanoic acid)3, Nd(2,2-dioctyldecanoic acid)3, Nd(2-ethyl-2-propyldecanoic acid)3, Nd(2-ethyl-2-butyldecanoic acid)3, Nd(2-ethyl-2-hexyldecanoic acid)3, Nd(2-propyl-2-butyldecanoic acid)3, Nd(2-propyl-2-hexyldecanoic acid)3, Nd(2-propyl-2-isopropyldecanoic acid)3, Nd(2-butyldecanoic acid)3, Nd(2- One or more of the group consisting of 2-ethyl-2-hexyldecanoic acid)3, Nd(2-hexyl-2-octyldecanoic acid)3, Nd(2,2-diethyloctanoic acid)3, Nd(2,2-dipropyloctanoic acid)3, Nd(2,2-dibutyloctanoic acid)3, Nd(2,2-dihexyloctanoic acid)3, Nd(2-ethyl-2-propyloctanoic acid)3, Nd(2-ethyl-2-hexyloctanoic acid)3, Nd(2,2-diethylnonanoic acid)3, Nd(2,2-dipropylnonanoic acid)3, Nd(2,2-dibutylnonanoic acid)3, Nd(2,2-dihexylnonanoic acid)3, Nd(2-ethyl-2-propylnonanoic acid)3 and Nd(2-ethyl-2-hexylnonanoic acid)3.

5. The method for preparing the catalyst composition according to claim 1, wherein: The alkylating agent is an alkyl aluminum compound represented by the following formula 2: [Formula 2] AlR 4 R 5 R 6 In formula 2, R 4 To R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, wherein R 4 To R 6 It is not entirely hydrogen and does not include tri-n-hexyl aluminum and tri-n-octylaluminum.

6. The method for preparing the catalyst composition according to claim 1, wherein: The alkylating agent is a dialkylaluminum hydride.

7. The method for preparing the catalyst composition according to claim 1, wherein: The pretreatment reaction in the step (S10), the alkylation in the step (S20), or the pretreatment reaction in the step (S10) and the alkylation in the step (S20) are performed by including a conjugated diene monomer.

8. The method for preparing the catalyst composition according to claim 1, wherein: The halogen compound is one or more selected from the group consisting of alkyl aluminum halides represented by the following formula 3 and alkyl aluminum sesquihalides represented by the following formula 4: [Formula 3] AlR 7 R 8 R 9 In formula 3, R 7 To R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, wherein R 7 To R 9 Not all of them are halogen groups, [Formula 4] In formula 4, R 10 To R 12 are each independently an alkyl group having 1 to 12 carbon atoms, and X1 to X3 are each independently a halogen group.

9. The method for preparing the catalyst composition according to claim 1, wherein: The halogen compound is one or more selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides.

10. The method for preparing the catalyst composition according to claim 1, wherein: The step (S20) is continuously performed in a plurality of reactors connected in series.

11. The method for preparing the catalyst composition according to claim 10, wherein: The alkylating agent is divided and injected into the plurality of reactors connected in series.

12. The method for preparing the catalyst composition according to claim 1, wherein: The step (S10), the step (S20) and the step (S30) are performed continuously.

13. A method for preparing a conjugated diene polymer, comprising the step of polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition prepared by the method for preparing a catalyst composition according to claim 1 to prepare a living polymer (S100).

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