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 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 - 0082986, filed on June 27, 2023, the entire contents of which are 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 concerns about energy conservation and environmental issues, there is a need to reduce the fuel consumption rate of automobiles. As a method for achieving this need, 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 in a single compound type, but exist in a hydrogen - bond type and / or oligomer type due to 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 contamination of catalyst preparation equipment.

[0009] U.S. Registered 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 process of manufacturing the catalyst system in a batch manner, 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 level 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 Registered 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 the 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 catalyst composition for polymerizing polybutadiene by pretreating the hydrogen-bonded lanthanide rare earth element compound and / or oligomeric lanthanide rare earth element compound that causes deterioration of the catalyst activity before or simultaneously with alkylation.

[0019] That is, 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 preparing a catalyst composition with improved catalyst activity by pre-treating the hydrogen-bonded lanthanide rare earth element compound and / or oligomeric 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: an alkylation step (S10) of mixing and reacting a lanthanide rare earth element compound with an alkylating agent; and a halogenation step (S20) of mixing and reacting the alkylated lanthanide rare earth element compound in the step (S10) with a halogen compound, wherein the step (S10) is carried out by including a pretreatment agent, or the lanthanide rare earth element compound in the step (S10) is a lanthanide rare earth element compound that has been pretreated by a pretreatment step (S1) for a hydrogen-bonded, oligomeric or a combination thereof lanthanide rare earth element compound, the pretreatment step (S1) performs a pretreatment reaction on the hydrogen-bonded, oligomeric or a combination thereof of the lanthanide rare earth element compound, the pretreatment agent is one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, and the step (S1) 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.

[0024] (2) The present invention provides the method for preparing a catalyst composition according to (1), wherein the step (S1) is carried out before the lanthanide rare earth element compound is alkylated by 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, wherein 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-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl nonanoate)3, Nd(2,2-dihexyl nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3, and Nd(2-ethyl-2-hexyl nonanoate)3.

[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 6Not all are 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 the step (S1), the alkylation in the step (S10), or the pretreatment reaction in the step (S1) and the alkylation in the step (S10) 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 alkylaluminum halides represented by formula 3 and alkylaluminum sesquihalides 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 X3 are each independently 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 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 (9) to prepare a living polymer.

[0045] (11) The present invention provides a conjugated diene polymer prepared by a method for preparing a conjugated diene polymer according to (10).

[0046] (12) The present invention provides a rubber composition comprising the conjugated diene polymer according to (11).

[0047] Beneficial effects

[0048] 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 oligomer-type lanthanide rare earth element compound that cause deterioration of catalyst activity before alkylation, and has excellent catalyst activity.

[0049] 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, a high content of cis bonds and linearity, a narrow molecular weight distribution, and excellent abrasion resistance and low fuel consumption rate if applied to a rubber composition due to high catalyst activity. Detailed description of the invention

[0050] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0051] It will be understood that the words or terms used in the description 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 the words or terms to best explain the present invention, the words or terms should be construed as having meanings consistent with the technical idea of the present invention.

[0052] Method for preparing catalyst composition

[0053] The present invention provides a method for preparing a catalyst composition. The catalyst composition prepared by the method for preparing a catalyst composition can be a catalyst composition for polymerizing a conjugated diene polymer.

[0054] According to an embodiment of the present invention, the method for preparing a catalyst composition may include: an alkylation step (S10) of mixing and reacting a lanthanide rare earth element compound with an alkylating agent; and

[0055] A halogenation step (S20) of mixing and reacting the alkylated lanthanide rare earth element compound in the step (S10) with a halogen compound, wherein the step (S10) is carried out by including a pretreatment agent, or the lanthanide rare earth element compound in the step (S10) is a lanthanide rare earth element compound obtained by pretreating a hydrogen bond type, oligomer type or a combination thereof of lanthanide rare earth element compounds through a pretreatment step (S1), the pretreatment step (S1) performs a pretreatment reaction on the hydrogen bond type, oligomer type or a combination thereof of the lanthanide rare earth element compounds, the pretreatment agent is one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, and the step (S1) 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.

[0056] As described in the background art of the present invention, lanthanide rare earth element compounds do not exist in 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 (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 is immediately alkylated, compared with the case where the lanthanide rare earth element compound exists as a single compound, the alkylation takes 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 leading to deterioration of catalyst activity, and there may be a problem of increasing contamination of the catalyst preparation equipment. However, in the method for preparing the catalyst composition of the present invention, according to the step (S1), the hydrogen bond type lanthanide rare earth element compound and / or oligomer type lanthanide rare earth element compound is pretreated before alkylation, or according to the step (S10), the hydrogen bond type lanthanide rare earth element compound and / or oligomer type lanthanide rare earth element compound is pretreated during 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.

[0057] According to an embodiment of the present invention, if the pretreatment reaction of the lanthanide rare earth element compound according to step (S1) is carried out, step (S1) can be 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. 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 (S1) as in the present invention but simply used as alkylating agents, the target lanthanide rare earth element compound may only result in alkylation, which requires a long time for alkylation and causes the defect of insufficient alkylation. In this regard, step (S1) can be carried out until the time point just before alkylation of the lanthanide rare earth element compound by one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum starts. 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 pretreatment in step (S1).

[0058] According to an embodiment of the present invention, step (S1) can 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, or 10 mol or more and 20 mol or less, 19 mol or less, 18 mol or less, 17 mol or less, 16 mol or less, 15 mol or less, 14 mol or less, 13 mol or less, 12 mol or less, 11 mol or less, or 10 mol or less of one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum relative to 1 mol of the lanthanide rare earth element compound.

[0059] According to an embodiment of the present invention, step (S1) 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.

[0060] According to an embodiment of the present invention, step (S1) 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.

[0061] According to one embodiment of the present invention, by controlling the molar ratio of the lanthanide rare earth element compound to one or more trialkylaluminums 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 a hydrogen bond type, oligomer type, or a combination thereof in step (S1) can be further improved.

[0062] According to one embodiment of the present invention, the lanthanide rare earth element compound may be a neodymium compound, specifically neodymium carboxylate (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.); organic phosphate (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, neodymium didecyl phosphate, etc.); organic phosphonate (e.g., 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 hypophosphite (e.g., neodymium butylhypophosphite, neodymium pentylhypophosphite, neodymium hexylhypophosphite, neodymium heptylhypophosphite, neodymium octylhypophosphite, neodymium (1-methylheptyl)hypophosphite, neodymium (2-ethylhexyl)hypophosphite, etc.); carbamate (e.g., neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, neodymium dibenzylcarbamate, etc.); dithiocarbamate (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate, etc.); xanthate (e.g., neodymium methylxanthate, neodymium ethylxanthate, neodymium isopropylxanthate, neodymium butylxanthate, neodymium benzylxanthate, etc.); β-diketonate (e.g., neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylpyruvate, etc.); alkoxide or allyloxide (e.g., neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide, neodymium nonylphenoxide, etc.); halide or pseudohalide (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide, etc.); oxyhalide (e.g., neodymium oxyfluoride, neodymium oxychloride, neodymium oxybromide, etc.); or an organoneodymium compound containing one or more rare earth element-carbon bonds (e.g., Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, Ln(allyl)2Cl, 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.

[0063] According to one embodiment of the present invention, the lanthanide rare earth element compound may be a neodymium compound represented by Formula 1.

[0064] [Formula 1]

[0065]

[0066] 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 may be an alkyl group having 4 to 12 carbon atoms, and R 2 and R 3 may 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 may be an alkyl group having 6 to 8 carbon atoms, and R 2 and R 3 may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R 2 and R 3 are not all hydrogen.

[0067] According to one embodiment of the present invention, the lanthanide rare earth element compound may be one or more 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-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd(2-hexyl-2-octyl decanoate)3, Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl nonanoate)3, Nd(2,2-dihexyl nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3, and Nd(2-ethyl-2-hexyl nonanoate)3.

[0068] According to an 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 in the central part is reduced. Therefore, an effect of achieving a high conversion rate to the catalyst active species can be shown.

[0069] According to an 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 a 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.

[0070] According to an embodiment of the present invention, step (S1) 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 in advance 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.

[0071] According to an embodiment of the present invention, the conjugated diene monomer that can be injected in step (S1) may be 1,3-butadiene or its derivatives such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 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.

[0072] According to an embodiment of the present invention, if step (S1) 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.

[0073] According to an embodiment of the present invention, step (S10) is a step of alkylating the lanthanide rare earth element compound, and 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 in step (S1) with an alkylating agent, or by mixing and reacting the non-pre-treated lanthanide rare earth element compound with a pre-treating agent and an alkylating agent. Here, the non-pre-treated lanthanide rare earth element compound is the same as the above-mentioned lanthanide rare earth element compound.

[0074] According to an embodiment of the present invention, if step (S10) is carried out by including a pre-treating agent, then step (S10) can be carried out by mixing and reacting the lanthanide rare earth element compound, the pre-treating agent and the alkylating agent, and the pre-treating agent can carry out a pre-treatment reaction on the hydrogen bond type, oligomer type or a combination thereof of the lanthanide rare earth element compound. Tri-n-hexylaluminum and tri-n-octylaluminum are known to be used as alkylating agents in alkylation reactions. However, if tri-n-hexylaluminum and tri-n-octylaluminum are simply used as alkylating agents instead of for carrying out the pre-treatment reaction in step (S10) as in the present invention, alkylation of the lanthanide rare earth element compound may not be caused according to the purpose, which results in the defects that alkylation takes a long time and alkylation cannot be carried out sufficiently. 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 not be sufficient to cause a pre-treatment reaction on the hydrogen bond type, oligomer type or a combination thereof of the lanthanide rare earth element compound, and thus is not suitable as a pre-treating agent for the pre-treatment reaction in the alkylation process of step (S10).

[0075] According to an embodiment of the present invention, step (S10) can be carried out by injecting one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum at a molar ratio of 1 mol or more, 2 mol or more, 3 mol or more, 4 mol or more, 5 mol or more, 6 mol or more, 7 mol or more, 8 mol or more, 9 mol or more, 10 mol or more, 11 mol or more, 12 mol or more, 13 mol or more, 14 mol or more, 15 mol or more, 16 mol or more, 17 mol or more, 18 mol or more, 19 mol or more, or 20 mol or more based on 1 mol of the lanthanide rare earth element compound and at a molar ratio of 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, or 20 mol or less.

[0076] 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.

[0077] 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 for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0078] According to an embodiment of the present invention, by controlling the molar ratio, reaction temperature, and reaction time of the lanthanide rare earth element compound and one or more trialkylaluminums selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, the pretreatment reaction efficiency of the hydrogen bond type, oligomer type, or a combination thereof of the lanthanide rare earth element compound in step (S10) can be further improved.

[0079] According to an embodiment of the present invention, the alkylating agent can be an organometallic compound that can transfer a hydrocarbon group to another metal and can act as a cocatalyst. The alkylating agent can be an organometallic compound soluble in a polymer solvent and containing a metal-carbon bond, such as an organoaluminum compound, an organomagnesium compound, and an organolithium compound.

[0080] According to an embodiment of the present invention, the alkylating agent may be an organoaluminum compound, specifically, an alkylaluminum such as tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum; a 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; and a hydrocarbylaluminum dihydride such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

[0081] 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 (S1) or the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof by a pretreatment agent in step (S10), the alkylating agent may preferably be an alkylaluminum compound. In a specific embodiment, the alkylating agent may be an alkylaluminum compound represented by Formula 2.

[0082] [Formula 2]

[0083] AlR 4 R 5 R 6

[0084] 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 tri-n-hexylaluminum and tri-n-octylaluminum may not be included. 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 tri-n-hexylaluminum and tri-n-octylaluminum may not be included. In a more specific embodiment, in Formula 2, R 4 to R 6may each independently be hydrogen or an alkyl group having 3 to 5 carbon atoms, where R 4 to R 6 are not all hydrogen.

[0085] 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 (S1) or the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof by a pretreatment agent 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.

[0086] 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 trialkylaluminum. In a more specific embodiment, the alkylating agent may include diisobutylaluminum hydride and triisobutylaluminum.

[0087] According to an embodiment of the present invention, step (S10) 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 or the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof in step (S1).

[0088] According to an embodiment of the present invention, step (S10) 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.

[0089] 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 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.

[0090] According to an embodiment of the present invention, by controlling the molar ratio, reaction temperature, and reaction time of the lanthanide rare earth element compound or the pre-treated lanthanide rare earth element compound of the hydrogen bond type, oligomer type, or a combination thereof in step (S1) and the alkylating agent, the catalyst activity in step (S10) can be further improved.

[0091] According to an embodiment of the present invention, step (S10) can be carried out by including a conjugated diene monomer for the same purpose as in step (S1). In this case, if step (S1) is carried out by including a conjugated diene monomer, then step (S10) can be carried out by including a conjugated diene monomer separately or simultaneously with step (S1).

[0092] 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 or the pre-treated lanthanide rare earth element compound of the hydrogen bond type, oligomer type, or a combination thereof in step (S1), 1 mol or more, 5 mol or more, 10 mol or more, 15 mol or more, or 20 mol or more of the conjugated diene monomer can be injected, 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.

[0093] According to an embodiment of the present invention, step (S20) is a step of halogenating the alkylated lanthanide rare earth element compound in step (S10), and can be carried out by mixing and reacting the alkylated lanthanide rare earth element compound in step (S10) with a halogen compound.

[0094] 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.

[0095] According to an embodiment of the present invention, the diatomic halogen can include fluorine, chlorine, bromine, or iodine.

[0096] 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.

[0097] According to one embodiment of the present invention, the hydrogen halide may include hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide.

[0098] According to one embodiment of the present invention, the organic halide may include tert-butyl chloride (t-BuCl), tert-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chlorodiphenylmethane, bromodiphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzal chloride, benzal bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, methyl iodide, diiodomethane, triiodomethane (also known as "iodoform"), tetraiodomethane, 1-iodopropane, 2-iodopropane, 1,3-diiodopropane, tert-butyl iodide, 2,2-dimethyl-1-iodopropane (also known as "neopentyl iodide"), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, 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.

[0099] According to one embodiment of the present invention, the non-metal halide may include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphoryl chloride, phosphoryl bromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl4), silicon tetrabromide, arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphoryl iodide, or selenium tetraiodide.

[0100] 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.

[0101] 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, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, 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, methylaluminum diiodide, ethylaluminum diiodide, n-butylaluminum diiodide, isobutylaluminum diiodide, 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.

[0102] 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.

[0103] [Formula 3]

[0104] AlR 7 R 8 R 9

[0105] 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 R 9 are not all halogen groups. In a specific embodiment, in Formula 3, R 7 to R 9 may each independently be a halogen group or an alkyl group having 1 to 6 carbon atoms, wherein R 7 to R 9 are not all halogen groups. In a more specific embodiment, in Formula 3, R 7 and R 8 may each independently be an alkyl group having 1 to 4 carbon atoms, and R 9It may be a halogen group.

[0106] [Formula 4]

[0107]

[0108] In Formula 4, R 10 to R 12 may each independently be an alkyl group having 1 to 12 carbon atoms, and X1 to X3 may each independently be a halogen group. In a specific embodiment, in Formula 4, R 10 to R 12 may 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 may each independently be an alkyl group having 1 to 4 carbon atoms.

[0109] According to one 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 (S1) or the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof by a pretreatment agent in step (S10), the halogen compound may be one or more selected from the group consisting of dialkyl aluminum halide and alkyl sesquialuminum halide, and the types of dialkyl aluminum halide and alkyl sesquialuminum halide are the same as those described above. In a specific embodiment, the dialkyl aluminum halide may be diethyl aluminum chloride, and the alkyl sesquialuminum halide may be ethyl sesquichloride.

[0110] According to one embodiment of the present invention, step (S20) may 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 or the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type, or a combination thereof in step (S1).

[0111] According to one embodiment of the present invention, step (S20) may 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.

[0112] According to an embodiment of the present invention, step (S20) can be carried out for more than 10 minutes, more than 15 minutes, more than 20 minutes, more than 25 minutes, or more than 30 minutes and less than 1 hour, less than 50 minutes, less than 40 minutes, or less than 30 minutes.

[0113] According to an embodiment of the present invention, by taking into account the molar ratio of the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type or a combination thereof in control step (S1) or the lanthanide rare earth element compound pretreated with a hydrogen bond type, oligomer type or a combination thereof by a pretreatment agent in step (S10) to the alkylating agent, the reaction temperature and the reaction time, the catalyst activity can be further improved in step (S20).

[0114] According to an embodiment of the present invention, steps (S1), (S10) and (S20) 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.

[0115] According to an embodiment of the present invention, steps (S1), (S10) and (S20) can be carried out in a batch reactor. In addition, steps (S1), (S10) and (S20) can be carried out by sequentially injecting the lanthanide rare earth element compound, trialkylaluminum, alkylating agent and halogen compound according to each step.

[0116] According to an embodiment of the present invention, steps (S1), (S10) and (S20) can each be carried out in a separate reactor connected in series. Therefore, in order to continuously prepare the catalyst according to the preparation method of the catalyst composition, two or more reactors may be required.

[0117] According to an embodiment of the present invention, steps (S1), (S10), and (S20) can be carried out continuously. That is, steps (S1), (S10), and (S20) 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, step (S10) can be carried out continuously in a plurality of reactors connected in series. In this case, since the alkylation is carried out in a plurality of reactors connected in series, the alkylation can be carried out sufficiently, and the activity of the catalyst composition can be further increased. In this case, the pretreatment agent and / or the alkylating agent can be injected only into the first reactor of the plurality of reactors connected in series to carry out step (S10), and can be separated and injected into the plurality of reactors connected in series to carry out step (S10). If the pretreatment agent and / or the alkylating agent are separated and injected into a plurality of reactors, the reactors into which the pretreatment agent and / or the alkylating agent are injected can be selected as needed. In addition, the types of the pretreatment agent and / or the alkylating agent separated and injected into the plurality of reactors connected in series can be the same as or different from each other.

[0119] According to an embodiment of the present invention, at least one of the plurality of reactors connected in series in step (S10) may include a tubular reactor provided with a line mixer. In this case, the reactants may remain in the tubular reactor connected between the reactors connected in series, and continuous mixing may be carried out, so that the alkylation can be carried out more sufficiently.

[0120] According to an embodiment of the present invention, all steps of the method for preparing the catalyst composition including steps (S1), (S10), and (S20) 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.

[0121] According to an embodiment of the present invention, all steps of the method for preparing the catalyst composition including steps (S1), (S10), and (S20) can be carried out for 30 minutes or longer, 35 minutes or longer, 40 minutes or longer, 45 minutes or longer, 50 minutes or longer, 55 minutes or longer, 60 minutes or longer, 65 minutes or longer, or 70 minutes or longer and 2 hours or shorter, 1 hour 50 minutes or shorter, 1 hour 40 minutes or shorter, 1 hour 30 minutes or shorter, 1 hour 20 minutes or shorter, or 1 hour 10 minutes or shorter.

[0122] Method for preparing conjugated diene polymer

[0123] The present invention provides a method for preparing a conjugated diene polymer.

[0124] According to one embodiment of the present invention, the method for preparing a conjugated diene polymer may include a step (S100) of polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition prepared by a method for preparing a catalyst composition to prepare a living polymer.

[0125] According to one 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.

[0126] According to one 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.

[0127] According to one embodiment of the present invention, the catalyst composition may be a catalyst composition prepared by the above 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 a neodymium compound.

[0128] According to one 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 constant temperature polymerization (adiabatic polymerization).

[0129] According to one embodiment of the present invention, constant temperature polymerization may refer to polymerization that uses the self-generated reaction heat without arbitrarily applying heat after injecting the catalyst composition, and heat polymerization may refer to injecting the catalyst composition and then increasing the temperature by arbitrarily applying heat. Isothermal polymerization may refer to adding heat or removing heat after adding the catalyst composition to keep the temperature of the reactants constant.

[0130] According to an embodiment of the present invention, the polymerization in step (S100) can be carried out by coordination anionic polymerization, and the polymerization environment can be bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, specifically solution polymerization.

[0131] According to an embodiment of the present invention, the polymerization in step (S100) can be carried out at a temperature above -20°C, above -10°C, above 0°C, above 10°C, above 20°C, above 30°C, above 40°C, above 50°C, or above 60°C and below 200°C, below 150°C, below 120°C, or below 90°C. Within this range, the polymerization reaction can be smoothly controlled, and the cis-1,4 bond content of the conjugated diene polymer thus produced can be ensured.

[0132] According to an embodiment of the present invention, the polymerization in step (S100) can be carried out for 15 minutes or more, 20 minutes or more, 30 minutes or more, 40 minutes or more, 50 minutes or more, or 1 hour or more and 3 hours or less, 2 hours 30 minutes or less, or 2 hours or less.

[0133] 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 part activated by the catalyst composition.

[0134] According to an embodiment of the present invention, step (S200) of reacting the active polymer with a modifier can 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.

[0135] According to an embodiment of the present invention, the method for preparing a conjugated diene polymer can include, after preparing the active polymer, completing the polymerization by further using additives such as polyethylene glycol phosphate, etc., as reaction quenching agents for completing the polymerization reaction and antioxidants such as 2,6-di-tert-butyl-p-cresol, etc. In addition, additives commonly used to promote solution polymerization, such as chelating agents, dispersants, pH control agents, deoxidizing agents, and oxygen scavengers, etc., can be selectively further used together with the reaction quenching agent.

[0136] Conjugated diene polymer

[0137] The present invention provides a conjugated diene polymer.

[0138] 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 catalyst composition.

[0139] 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.

[0140] 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 can be used.

[0141] 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.

[0142] 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, 5.0×105 less than g / mol, 4.0×10 5 less than g / mol, or 3.0×10 5 less 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 less than g / mol, 5.0×10 5 less than g / mol, 4.0×10 5 less than g / mol, 3.0×10 5 less than g / mol, 2.0×10 5 less than g / mol, or 1.0×10 5 less than g / mol. 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, an excellent balance of mechanical and physical properties of the rubber composition can be achieved.

[0143] 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).

[0144] According to one 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 an excellent balance of physical properties can be achieved.

[0145] According to an embodiment of the present invention, the content of cis-1,4 bonds in the conjugated diene polymer may be 96.0% by weight or more, 96.1% by weight or more, 96.2% by weight or more, 96.3% by weight or more, 96.4% by weight or more, 96.5% by weight or more, 96.6% by weight or more, 96.7% by weight or more, 96.8% by weight or more, 96.9% by weight or more, 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, 97.9% by weight or more, 98.0% by weight or more, 98.1% by weight or more, or 98.2% by weight or more and 100.0% by weight or less, 99.5% by weight or less, or 99.0% by weight or less.

[0146] According to an embodiment of the present invention, the Mooney viscosity (ML1+4, @100 °C) of the conjugated diene polymer may be 30 or more, 31 or more, 32 or more, 33 or more, 34 or more, 35 or more, 36 or more, 37 or more, 38 or more, 39 or more, 40 or more, 41 or more, 42 or more, or 43 or more and 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, 49 or less, 48 or less, or 47 or less.

[0147] Rubber composition

[0148] The present invention provides a rubber composition.

[0149] 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 the conjugated diene polymer in an amount of 0.1% by weight or more, 10% by weight or more, or 20% by weight or more and 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 a molded article such as a tire manufactured using the rubber composition can be sufficiently ensured.

[0150] 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 components may be 90% by weight or less based on the total weight of the rubber composition. Specifically, the content of the rubber components may be 1 part by weight to 900 parts by weight relative to 100 parts by weight of the conjugated diene copolymer.

[0151] According to an embodiment of the present invention, the rubber component may be natural rubber or synthetic rubber. For example, natural rubber (NR) including 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, acryl 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.

[0152] According to an embodiment of the present invention, with respect 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.

[0153] 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. In addition, the dibutyl phthalate oil absorption amount (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.

[0154] 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 breaking characteristics and the wet grip. In addition, 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), 100 m 2 / g to 200 m2 The 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.

[0155] According to an 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-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyl dimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, or dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide. In a specific embodiment, considering the improvement effect of the reinforcing performance, the silane coupling agent can be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide.

[0156] According to an 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.

[0157] According to an 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.

[0158] 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.

[0159] 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 oil can be used, and considering the hysteresis loss and performance at low temperatures, naphthenic or paraffin-based processing oil 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 release performance (low fuel consumption rate) of the vulcanized rubber can be prevented.

[0160] 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.

[0161] According to an embodiment of the present invention, the rubber composition can be obtained by kneading using kneading equipment such as a Banbury mixer, a roll, and an internal mixer according to a mixing formula. In addition, a rubber composition having low heat release performance and excellent abrasion resistance can be obtained through a vulcanization process after a molding process.

[0162] 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 coating rubber, a bead filler, a bead wrapper, and a bead coating rubber, or to manufacture rubber products in various industries, such as vibration-proof 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.

[0163] 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.

[0164] Examples and Comparative Examples

[0165] Example 1

[0166] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 1.3 g of tri - n - octylaluminum and 0.8 g of diisobutylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0167] Example 2

[0168] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 1.0 g of tri - n - hexylaluminum and 0.8 g of diisobutylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0169] Example 3

[0170] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 1.3 g of tri - n - octylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.8 g of diisobutylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0171] Example 4

[0172] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 1.0 g of tri - n - octylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 2.1 g of triisobutylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0173] Example 5

[0174] Inject 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n-hexane into it. Then, inject 2.6 g of tri-n-octylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.8 g of diisobutylaluminum hydride into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at -5 °C and stir for 30 minutes to prepare the catalyst composition.

[0175] Example 6

[0176] Inject 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n-hexane into it. Then, inject 1.3 g of tri-n-octylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.8 g of diisobutylaluminum hydride into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of ethyl sesquichloride into the reactor at -5 °C and stir for 30 minutes to prepare the catalyst composition.

[0177] Example 7

[0178] Inject 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n-hexane into it. Then, inject 1.0 g of tri-n-hexylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.8 g of diisobutylaluminum hydride into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at -5 °C and stir for 30 minutes to prepare the catalyst composition.

[0179] Example 8

[0180] Inject 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n-hexane into it. Then, inject 1.0 g of tri-n-hexylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 2.1 g of triisobutylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at -5 °C and stir for 30 minutes to prepare the catalyst composition.

[0181] Example 9

[0182] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 2.0 g of tri - n - hexylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.8 g of diisobutylaluminum hydride into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0183] Example 10

[0184] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 1.0 g of tri - n - hexylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.8 g of diisobutylaluminum hydride into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of ethyl sesquichloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0185] Comparative Example 1

[0186] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 0.8 g of diisobutylaluminum hydride into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0187] Comparative Example 2

[0188] Inject 2.1 g of 1,3 - butadiene diluted to a concentration of 4.5 wt% in n - hexane into the reactor, and inject 0.6 g of neodymium versatate (Solvay) diluted to a concentration of 40 wt% in n - hexane into it. Then, inject 2.1 g of tri - isobutylaluminum into the reactor at 10 °C and stir for 30 minutes. Then, inject 0.1 g of diethylaluminum chloride into the reactor at - 5 °C and stir for 30 minutes to prepare the catalyst composition.

[0189] Experimental Example

[0190] Experimental Example 1: Preparation of Conjugated Diene Polymer and Evaluation of Catalyst Composition Activity

[0191] 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 3 to 10 were used, 0.10 g of diisobutylaluminum hydride was added to the reactor as a molecular weight regulator, or if the catalyst compositions prepared in Examples 1, 2, Comparative Example 1, and Comparative Example 2 were used, 0.25 g of diisobutylaluminum hydride was added as a molecular weight regulator, and then each catalyst composition prepared in Examples 1 to 10 and Comparative Examples 1 and 2 was injected, followed by polymerization. At the time point when the polymerization conversion reached over 98%, 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 placed in hot water heated by steam and stirred to remove the solvent. The resulting product was roll-dried to remove residual solvent and water, thereby preparing a butadiene polymer.

[0192] 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 was calculated according to the following Equation 1. For each catalyst composition of Examples 1 to 10, Comparative Example 1, and Comparative Example 2, the polymerization conversion 25 minutes after the start of the reaction was measured, and the activities of the catalyst compositions were evaluated and shown in Table 1. Based on the measured value of Comparative Example 1 as a reference value, the activities of the catalyst compositions of the examples and comparative examples were indexed using Equation 2.

[0193] In addition, the performances of the catalyst compositions prepared in Examples 1 to 10 and Comparative Examples 1 and 2 were visually evaluated, and the morphologies are shown together in Tables 1 and 2 below.

[0194] [Equation 1]

[0195] Polymerization conversion (%) = TSC (%) of the sample / Concentration (wt%) of the injected 1,3-butadiene

[0196] [Equation 2]

[0197] Activity index = (Measured value / Reference value) × 100

[0198] [Table 1]

[0199]

[0200] [Table 2]

[0201]

[0202] As shown in Tables 1 and 2, it was confirmed that the catalyst compositions prepared in Examples 1 to 10 exhibited the performance of a catalyst solution in a transparent liquid phase, thus ensuring the preparation of the catalyst composition and showing a very high activity of the catalyst composition as compared with Comparative Examples 1 and 2.

[0203] Specifically, it was confirmed that the catalyst compositions prepared in Examples 3 to 10 showed a further improved activity of the catalyst composition by performing a pretreatment step before the alkylation of the lanthanide rare earth element compound.

[0204] On the contrary, in Comparative Examples 1 and 2 where the pretreatment step using tri-n-hexylaluminum and tri-n-octylaluminum was not carried out on the lanthanide rare earth element compound according to the present invention, it was confirmed that the activity of the catalyst composition decreased. Specifically, in the case of Comparative Example 1, it was confirmed that the activity of the catalyst composition decreased as compared with Examples 1 to 3, 5, 7, and 9 using the same alkylating agent and halogen compound, and in the case of Comparative Example 2, it was directly confirmed that the activity of the catalyst composition decreased as compared with Examples 4 and 8 using the same alkylating agent and halogen compound.

[0205] Experimental Example 2: Evaluation of Physical Properties of Conjugated Diene Polymers

[0206] For the conjugated diene polymers prepared using the catalyst compositions of Examples 1 to 10 and Comparative Examples 1 and 2 in Experimental Example 1, the Mooney viscosity, molecular weight distribution, and cis-1,4 bond content were measured as follows and shown in Tables 3 and 4 below.

[0207] * 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 Company. 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.

[0208] * 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) from Polymer laboratories company and one PLgel mixed-C column were used in combination. In addition, the newly replaced columns were all mixed-bed type columns, and polystyrene was used as the GPC standard material.

[0209] *Cis-1,4 bond content: The cis-1,4 bond content of the conjugated diene moiety 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 -1 for the trans-1,4 bond, the minimum peak (c) at approximately 911 cm -1 for the vinyl bond, and the minimum peak (d) at approximately 736 cm -1 for the cis-1,4 bond to obtain each content.

[0210] [Table 3]

[0211] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Mooney viscosity (MU) 32 32 45 47 41 46 Molecular weight distribution 3.0 3.0 2.3 2.4 2.3 2.4 Content of cis-1,4 bond (wt%) 96.2 96.2 98.3 97.9 97.1 98.0

[0212] [Table 4]

[0213] Classification Example 7 Example 8 Example 9 Example 10 Comparative Example 1 Comparative Example 2 Mooney viscosity (MU) 43 45 40 44 45 48 Molecular weight distribution 2.3 2.4 2.3 2.4 2.9 3.1 Content of cis-1,4 bond (wt%) 98.2 97.9 97.1 98.1 97.5 97.1

[0214] As shown in Tables 3 and 4, it was confirmed that the conjugated diene polymers prepared using the catalyst compositions prepared in Examples 1 to 10 exhibited an appropriate level of Mooney viscosity while ensuring a high level of cis-1,4 bond content. Specifically, it was confirmed that the conjugated diene polymers prepared using the catalyst compositions prepared in Examples 3, 4, 6 to 8, and 10 exhibited excellent Mooney viscosity, molecular weight distribution, and cis-1,4 bond content.

[0215] In contrast, it was confirmed that compared with Examples 3, 4, 6 to 8, and 10, the conjugated diene polymers prepared using the catalyst compositions prepared in Comparative Examples 1 and 2 exhibited a broad molecular weight distribution and a reduced cis-1,4 bond content.

[0216] Experimental Example 3: Evaluation of Physical Properties of Rubber Compositions

[0217] Using the conjugated diene polymers prepared using the catalyst compositions of Examples 1 to 10 and Comparative Examples 1 and 2 in Experimental Example 1, rubber compositions and rubber specimens were prepared, and the Mooney viscosity, abrasion resistance, tensile properties, and viscoelastic properties of the rubber compositions were measured by the following methods and are shown in Tables 5 and 6 below.

[0218] <Preparation of Rubber Compositions and Rubber Specimens>

[0219] For each conjugated diene polymer prepared using the catalyst compositions of Examples 1 to 10 and Comparative Examples 1 and 2 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 relative to 100 parts by weight of the polymer.

[0220] Then, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), and 0.5 parts 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. A sheet-like vulcanized blend was formed using a roll at 50 °C. The vulcanized blend was vulcanized at 160 °C for 25 minutes to form a rubber specimen.

[0221] * Tensile properties: Each prepared rubber composition was vulcanized at 150 °C for t90 minutes, and then based on ASTM D412, the modulus (M-300%, kg·f / cm 2 ) when the vulcanized product was elongated by 300% was measured. Based on the measured value of Comparative Example 1 as a reference value, the 300% modulus of the examples and comparative examples was indexed using Equation 3.

[0222] [Equation 3]

[0223] M-300% index = (measured value / reference value) x 100

[0224] * Viscoelastic properties: The viscoelastic property coefficient (tanδ) was measured from -60 °C to 60 °C at a frequency of 10 Hz, a prestrain of 3%, and a dynamic strain of 3% using a DMTS 500N from GABO (Germany). In this case, the tanδ value at 0 °C represents skid resistance, and the tanδ value at 60 °C represents rolling resistance (fuel consumption rate). Based on the measured value of Comparative Example 1 as a reference value, the viscoelastic properties of the examples and comparative examples were indexed using Equation 4.

[0225] [Equation 4]

[0226] Tanδ60 °C index = (reference value / measured value) x 100

[0227] * Abrasion resistance: Each formed rubber specimen was subjected to a DIN wear test based on ASTM D5963 and shown as a DIN weight loss index (loss volume index: abrasion resistance index (ARIA, Method A)). Based on the measured value of Comparative Example 1 as a reference value, the abrasion resistance of the examples and comparative examples was indexed using Equation 5.

[0228] [Equation 5]

[0229] Wear amount index = (reference value / measured value) x 100

[0230] [Table 5]

[0231]

[0232] [Table 6]

[0233]

[0234] As shown in Tables 5 and 6, it can be confirmed that, compared with the rubber composition prepared by including the conjugated diene polymer prepared using the catalyst composition prepared in Comparative Example 1, the rubber compositions prepared by including the conjugated diene polymers prepared using the catalyst compositions prepared in Examples 1 to 10 all showed improved tensile properties, viscoelastic properties, and abrasion resistance. Specifically, the rubber compositions prepared by including the conjugated diene polymers prepared using the catalyst compositions prepared in Examples 3 to 10 all showed significantly improved tensile properties, viscoelastic properties, and abrasion resistance.

[0235] On the contrary, it can be confirmed that, compared with the rubber composition prepared by including the conjugated diene polymer prepared using the catalyst composition prepared in Comparative Example 1, the rubber composition prepared by including the conjugated diene polymer prepared using the catalyst composition prepared in Comparative Example 2 showed deteriorated tensile properties, viscoelastic properties, and abrasion resistance.

[0236] This result was obtained as follows: In the process of preparing the catalyst composition for preparing the conjugated diene polymer, the catalyst activity was improved by pretreating the hydrogen-bonded lanthanide rare earth element compound and / or oligomer-type lanthanide rare earth element compound that cause deterioration of the catalyst activity before or simultaneously with alkylation.

[0237] From the results, it can be confirmed that the catalyst composition prepared according to the preparation method of the catalyst composition of the present invention shows excellent catalyst activity by pretreating the hydrogen-bonded lanthanide rare earth element compound and / or oligomer-type lanthanide rare earth element compound that cause deterioration of the catalyst activity before or simultaneously with alkylation.

[0238] In addition, it can be confirmed that the conjugated diene polymer prepared according to the preparation method of the conjugated diene polymer of the present invention has a small content of lanthanide rare earth elements remaining in the conjugated diene polymer, a high cis-bond content and linearity, a narrow molecular weight distribution due to high catalyst activity, and excellent abrasion resistance and fuel consumption if applied to a rubber composition.

Claims

1. A method for preparing a catalyst composition, the method comprising: an alkylation step (S10) of mixing and reacting a lanthanide rare earth element compound with an alkylating agent; as well as a halogenation step (S20) of mixing and reacting the lanthanide rare earth element compound alkylated in step (S10) with a halogen compound, Wherein, the step (S10) is performed by including a pretreatment agent, or The lanthanide rare earth element compound in the step (S10) is a lanthanide rare earth element compound that has been pretreated in a hydrogen bond type, an oligomer type or a combination thereof by a pretreatment step (S1), wherein the pretreatment step (S1) performs a pretreatment reaction on the hydrogen bond type, the oligomer type or a combination thereof of the lanthanide rare earth element compound. The pretreatment agent is one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, and The step (S1) is performed 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.

2. The method for preparing the catalyst composition according to claim 1, wherein: The step (S1) is performed before the lanthanide rare earth element compound is alkylated with 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-hexylaluminum 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 (S1), the alkylation in the step (S10), or the pretreatment reaction in the step (S1) and the alkylation in the step (S10) 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. 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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