Catalyst composition preparation method and conjugated diene-based polymer preparation method

Abstract

The present invention relates to: a catalyst composition preparation method for continuously preparing a catalyst composition with improved catalytic activity, the method pre-treating a hydrogen-bonded lanthanide rare earth element compound and / or an oligomeric form of a lanthanide rare earth element compound which causes a decrease in catalytic activity; and a conjugated diene-based polymer preparation method using the catalyst composition prepared the method.

Description

Method for preparing a catalyst composition and method for preparing a conjugated diene polymer

[0001] [Cross-citation with related applications]

[0002] This invention claims the benefit of priority to Korean Patent Application No. 10-2023-0082987, filed June 27, 2023, the entire contents of which are incorporated herein by reference.

[0003] [Technical Field]

[0004] The present invention relates to a method for producing a catalyst composition for producing a conjugated diene polymer and a method for producing a conjugated diene polymer using the same.

[0005] With growing interest in energy conservation and environmental issues, there is a growing demand for improved fuel efficiency in automobiles. One approach to achieving this goal has been proposed: increasing the cis bond content and linearity of polybutadiene in tire-forming rubber compositions while narrowing the molecular weight distribution.

[0006] Polybutadiene can be produced using a Ziegler-Natta catalyst, and the Ziegler-Natta catalyst is produced by activating an organic acid metal compound with an alkyl aluminum and a halogenated alkyl aluminum compound, and reacting the produced catalyst with a 1,3-butadiene monomer to produce polybutadiene.

[0007] Here, the organic acid metal compounds include titanium-based, nickel-based, cobalt-based, and lanthanum-based compounds, and lanthanum-based rare earth element compounds are mainly used from the viewpoint of increasing the cis bond content and linearity of polybutadiene while narrowing the molecular weight distribution.

[0008] Representative examples of the above lanthanide rare earth element compounds include neodymium compounds, and specific examples include NdV (neodymium versatate). These are activated through an alkylation reaction using an alkyl aluminum compound, followed by a halogenation reaction using a halogenated alkyl aluminum compound. In order to stabilize the catalyst, a 1,3-butadiene monomer is added during the alkylation reaction to perform preforming.

[0009] At this time, lanthanide rare earth element compounds such as NdV do not exist in the form of a single compound, but exist in a hydrogen-bonded form and / or an oligomer form due to moisture and the aliphatic compound used in the manufacturing process (Non-patent Document 1 and Non-patent Document 2). However, if an alkylation reaction is directly performed on the hydrogen-bonded lanthanide rare earth element compound and / or the oligomer form of the lanthanide rare earth element compound, the alkylation takes a longer time than when the lanthanide rare earth element compound exists as a single compound, and there is a problem that the alkylation reaction does not proceed sufficiently. If a lanthanide rare earth element compound that has not been sufficiently alkylated is introduced into a halogenation reactor for performing a halogenation reaction, it causes a decrease in catalytic activity and also increases contamination of the catalyst manufacturing device.

[0010] U.S. Patent Publication No. 9,056,303 (Patent Document 1) discloses a method for producing a catalyst system using a plurality of alkylation reactors. Patent Document 1 is characterized by specifically specifying the type of reactor, controlling the flow rate of the outlet of the catalyst system at the line outlet as necessary, and allowing the reactor to remain within a residence time range suitable for the alkylation reaction and the chlorination reaction, in order to overcome the shortcomings of manufacturing the catalyst system in batch mode, when manufacturing continuously, and preventing gel formation within the reactor, and ensuring the flexibility of the alkylating agent and the salt of the rare earth element that affect the catalyst activity. In addition, Japanese Patent Publication No. 5,072,191 (Patent Document 2) discloses a method for producing a catalyst for conjugated diene polymerization, in which an alkyl aluminum compound and an alkyl aluminum hydride for the alkylation reaction are sequentially introduced. However, patent documents 1 and 2 only directly carry out an alkylation reaction on a lanthanum compound when manufacturing a catalyst system and a catalyst for conjugated diene polymerization, and do not recognize the form of the lanthanum compound introduced during the alkylation reaction and its influence on the catalytic activity.

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] (Patent Document 1) US 9056303 B2

[0014] (Patent Document 2) JP 5072191 B2

[0015] [Non-patent literature]

[0016] (Non-patent Document 1) “A Highly Reactive and Monomeric Neodymium Ctalyst”, Macromolecules 2002, 35, 13, 4875-4879 (https: / doi.org / 10.1021 / ma012123p)

[0017] (Non-patent Document 2) “Living and non-living Ziegler-Natta catalysts: electronic properties of active site”, Polymer, Volume 44, Issue 21, October 2003, Pages 6555-6558 (https: / doi.org / 10.1016 / S0032-3861(03)00698-0)

[0018] The problem to be solved in the present invention is to improve the catalytic activity by pretreating the hydrogen-bonded lanthanide rare earth element compound and / or the oligomeric form of the lanthanide rare earth element compound, which causes a decrease in catalytic activity, prior to the alkylation reaction in the continuous production of a catalyst composition for polymerization of polybutadiene.

[0019] That is, the present invention aims to provide a continuous manufacturing method for manufacturing a catalyst composition having improved catalytic activity by pre-treating a hydrogen-bonded lanthanide rare earth element compound and / or an oligomer form of a lanthanide rare earth element compound that causes a decrease in catalytic activity, in order to solve the problems mentioned in the background technology of the above invention.

[0020] In addition, the present invention aims to provide a method for producing a conjugated diene polymer having a high cis bond content and linearity and a narrow molecular weight distribution using a catalyst composition produced from the above catalyst composition production method.

[0021] To solve the above problem, the present invention provides a method for producing a catalyst composition and a method for producing a conjugated diene polymer.

[0022] (1) The present invention provides a method for preparing a catalyst composition, comprising a pretreatment step (S10) of performing a pretreatment reaction for a lanthanide rare earth element compound in the form of a hydrogen bond, an oligomer, or a combination thereof; an alkylation reaction step (S20) of mixing and reacting the lanthanide rare earth element compound, which has been pretreated in the form of a hydrogen bond, an oligomer, or a combination thereof in the step (S10), with an alkylating agent; and a halogenation reaction step (S30) of mixing and reacting the lanthanide rare earth element compound alkylated in the step (S20) with a halide, wherein the step (S10) is performed by mixing and reacting the lanthanide rare earth element compound with at least one trialkyl aluminum selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum, and wherein the steps (S10), (S20), and (S30) are each performed in a separate reactor connected in series.

[0023] (2) The present invention provides a method for producing a catalyst composition, wherein, in the above (1), the step (S10) is performed before an alkylation reaction by trialkyl aluminum occurs for a lanthanide series rare earth element compound.

[0024] (3) The present invention provides a method for producing a catalyst composition in (1) or (2), wherein the lanthanide series rare earth element compound is a neodymium compound represented by the following chemical formula 1.

[0025] [Chemical Formula 1]

[0026]

[0027] In the above chemical formula 1, R 1 Inland R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 Inland R 3 Not all of these are hydrogen.

[0028] (4) The present invention is any one of the above (1) to (3), wherein the lanthanide series rare earth element compound is Nd(2-ethyl hexanoate)3, Nd(2,2-dimethyl decanoate)3, Nd(2,2-diethyl decanoate)3, Nd(2,2-dipropyl decanoate)3, Nd(2,2-dibutyl decanoate)3, Nd(2,2-dihexyl decanoate)3, Nd(2,2-dioctyl decanoate)3, Nd(2-ethyl-2-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd(2-hexyl-2-octyl decanoate)3, Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl A method for producing a catalyst composition is provided, wherein the catalyst composition comprises at least one selected from the group consisting of Nd(2,2-dihexyl nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3, and Nd(2-ethyl-2-hexyl nonanoate)3.

[0029] (5) The present invention provides a method for producing a catalyst composition, wherein in any one of (1) to (4), the alkylating agent is an alkyl aluminum compound represented by the following chemical formula 2.

[0030] [Chemical Formula 2]

[0031] AlR 4 R 5 R 6

[0032] In the above chemical formula 2, R 4 Inland R 6are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 4 Inland R 6 Not all of these are hydrogen, and do not include tri-n-hexyl aluminum and tri-n-octyl aluminum.

[0033] (6) The present invention provides a method for producing a catalyst composition according to any one of the above (1) to (5), wherein the alkylating agent is a dialkyl aluminum hydride.

[0034] (7) The present invention provides a method for producing a catalyst composition, wherein in any one of the above (1) to (6), the pretreatment reaction of the step (S10), the alkylation reaction of the step (S20), or the pretreatment reaction of the step (S10) and the alkylation reaction of the step (S20) are carried out by including a conjugated diene monomer.

[0035] (8) The present invention provides a method for producing a catalyst composition, wherein in any one of the above (1) to (7), the halide is at least one selected from the group consisting of an alkyl aluminum halide represented by the following chemical formula 3 and an alkyl aluminum sesquihalide represented by the following chemical formula 4.

[0036] [Chemical Formula 3]

[0037] AlR 7 R 8 R 9

[0038] In the above chemical formula 3, R 7 Inland R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R 7 Inland R 9 Not all of them are halogens,

[0039] [Chemical Formula 4]

[0040]

[0041] In the above chemical formula 4, R 10 Inland R12 are each independently an alkyl group having 1 to 12 carbon atoms, and X1 to X3 are each independently a halogen group.

[0042] (9) The present invention provides a method for producing a catalyst composition, wherein in any one of the above (1) to (8), the halide is at least one selected from the group consisting of dialkyl aluminum halides and alkyl aluminum sesquihalides.

[0043] (10) The present invention provides a method for producing a catalyst composition, wherein the step (S20) is continuously performed in a plurality of reactors connected in series, in any one of the above (1) to (9).

[0044] (11) The present invention provides a method for producing a catalyst composition, wherein, in the above (10), the alkylating agent is divided and injected into a plurality of reactors connected in series.

[0045] (12) The present invention provides a method for producing a catalyst composition, wherein steps (S10), (S20), and (S30) are performed sequentially in any one of the above (1) to (11).

[0046] (13) The present invention provides a method for producing a conjugated diene polymer, including a step (S100) of producing an active polymer by polymerizing a conjugated diene monomer in the presence of a catalyst composition produced by a method for producing a catalyst composition according to any one of (1) to (12) above in a hydrocarbon solvent.

[0047] (14) The present invention provides a conjugated diene polymer manufactured by the conjugated diene polymer manufacturing method according to (13) above.

[0048] (15) The present invention provides a rubber composition comprising a conjugated diene polymer according to (14) above.

[0049] The catalyst composition manufactured according to the method for manufacturing a catalyst composition of the present invention has excellent catalytic activity by being manufactured by pretreating a hydrogen-bonded lanthanide rare earth element compound and / or an oligomer form of a lanthanide rare earth element compound that causes a decrease in catalytic activity prior to an alkylation reaction.

[0050] According to the method for producing a catalyst composition of the present invention, it is possible to continuously produce a catalyst composition, thereby improving the productivity of the catalyst composition and the conjugated diene polymer using the same, and ensuring more uniform quality.

[0051] The conjugated diene polymer produced according to the method for producing a conjugated diene polymer of the present invention has a low content of lanthanide rare earth elements remaining in the conjugated diene polymer due to high catalytic activity, a high cis bond content and linearity, a narrow molecular weight distribution, and, when applied to a rubber composition, exhibits excellent wear resistance and low fuel consumption.

[0052] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0053] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0054]

[0055] Method for preparing a catalyst composition

[0056] The present invention provides a method for preparing a catalyst composition. The catalyst composition prepared according to the method for preparing a catalyst composition may be a catalyst composition for polymerization of a conjugated diene polymer.

[0057] According to one embodiment of the present invention, the method for preparing the catalyst composition includes a pretreatment step (S10) of performing a pretreatment reaction for a lanthanide series rare earth element compound in a hydrogen bond, oligomer form, or a combination thereof; an alkylation reaction step (S20) of mixing and reacting the lanthanide series rare earth element compound, which has been pretreated in a hydrogen bond, oligomer form, or a combination thereof in step (S10), with an alkylating agent; and a halogenation reaction step (S30) of mixing and reacting the lanthanide series rare earth element compound alkylated in step (S20) with a halide, wherein step (S10) is performed by mixing and reacting the lanthanide series rare earth element compound with at least one trialkyl aluminum selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum, and wherein steps (S10), (S20), and (S30) may be performed in individual reactors connected in series, respectively.

[0058] As described in the background technology of the present invention, lanthanide rare earth element compounds do not exist in the form of a single compound, but exist in a hydrogen-bonded form and / or an oligomer form due to moisture and an aliphatic compound used in the manufacturing process (see Non-patent Documents 1 and 2). However, when an alkylation reaction is directly performed on a hydrogen-bonded lanthanide rare earth element compound and / or an oligomer form of a lanthanide rare earth element compound, the alkylation takes a longer time than when the lanthanide rare earth element compound exists as a single compound, and there is a problem that the alkylation reaction does not proceed sufficiently. When a lanthanide rare earth element compound that has not been sufficiently alkylated is introduced into a halogenation reactor for performing a halogenation reaction, it causes a decrease in catalytic activity and also causes a problem of increasing contamination of the catalyst manufacturing device. However, the method for manufacturing a catalyst composition according to the present invention can improve the catalytic activity by pretreating the hydrogen-bonded lanthanide series rare earth element compound and / or the oligomeric form of the lanthanide series rare earth element compound prior to the alkylation reaction according to the step (S10). Here, the pretreatment may mean minimizing, or even removing, the hydrogen-bonded lanthanide series rare earth element compound and / or the oligomeric form of the lanthanide series rare earth element compound prior to the alkylation reaction.

[0059] According to one embodiment of the present invention, the step (S10) may be carried out by mixing and reacting a lanthanide series rare earth element compound with at least one trialkyl aluminum selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum. It is known that the tri-n-hexyl aluminum and tri-n-octyl aluminum can be used as an alkylating agent for an alkylation reaction. However, when the tri-n-hexyl aluminum and tri-n-octyl aluminum are not used for the pretreatment reaction of the step (S10) as in the present invention, but are simply used as alkylating agents, the alkylation reaction for the lanthanide series rare earth element compound cannot be induced depending on the purpose, which causes the problem that the alkylation reaction takes a long time and the alkylation reaction does not proceed sufficiently. From this point of view, the step (S10) may be performed before an alkylation reaction occurs with at least one trialkyl aluminum selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum for the lanthanide series rare earth element compound. Meanwhile, trialkyl aluminum and / or dialkyl aluminum hydride that can be used as an alkylating agent other than tri-n-hexyl aluminum and tri-n-octyl aluminum cannot sufficiently induce a pretreatment reaction of hydrogen bonding, oligomer form, or a combination thereof for the lanthanide series rare earth element compound, and therefore are not suitable as a trialkyl aluminum compound for the pretreatment reaction of the step (S10).

[0060] According to one embodiment of the present invention, the step (S10) may be carried out by introducing at least one trialkyl aluminum selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum in a molar ratio of 1 mol or more, 2 mol or more, 3 mol or more, 4 mol or more, 5 mol or more, 6 mol or more, 7 mol or more, 8 mol or more, 9 mol or more, or 10 mol or more, with respect to 1 mol of the lanthanide series rare earth element compound, and may also be carried out by introducing at a molar ratio of 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.

[0061] According to one embodiment of the present invention, the step (S10) may be performed at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, and may also be performed 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.

[0062] According to one embodiment of the present invention, the step (S10) may be performed for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more, and may also be performed for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0063] According to one embodiment of the present invention, the step (S10) can further improve the efficiency of the pretreatment reaction of the hydrogen bond, oligomer form, or a combination thereof for the lanthanide rare earth element compound by controlling the molar ratio, reaction temperature, and reaction time between the lanthanide rare earth element compound and at least one trialkyl aluminum selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum.

[0064] According to one embodiment of the present invention, the lanthanide series rare earth element compound may be a neodymium compound, and specific examples thereof include neodymium carboxylates (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethyl hexanoate, neodymium neodecanoate, etc.); Organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl phosphate, etc.); Organophosphonates (e.g., neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium(1-methylheptyl) phosphonate, neodymium(2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate, or neodymium octadecyl phosphonate, etc.); Organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl) phosphinate, or neodymium (2-ethylhexyl) phosphinate); carbamates (e.g., neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate, or neodymium dibenzyl carbamate); dithiocarbamates (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate, or neodymium dibutyldithiocarbamate); Xanthogenates (e.g., neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl xanthogenate, or neodymium benzyl xanthogenate);β-diketonates (e.g., neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate, or neodymium benzoylacetonate); alkoxides or allyloxides (e.g., neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide, or neodymium nonyl phenoxide); halides or pseudohalides (e.g., neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); oxyhalides (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide); Or organic neodymium compounds containing one or more rare earth element-carbon bonds (e.g., Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, or Ln(allyl)2Cl, etc., where Ln is a rare earth metal element and R is a hydrocarbyl group), and the like, and may include any one or a mixture of two or more thereof.;

[0065] According to one embodiment of the present invention, the lanthanide series rare earth element compound may be a neodymium compound represented by the following chemical formula 1.

[0066] [Chemical Formula 1]

[0067]

[0068] In the above chemical formula 1, R 1 Inland R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 Inland R 3 All of these may not be hydrogen. As a specific example, in the above chemical formula 1, R 1 is an alkyl group having 4 to 12 carbon atoms, and R 2 and R3 Each independently represents hydrogen or an alkyl group having 2 to 8 carbon atoms, and R 2 and R 3 All of these may not be hydrogen. For a more specific example, in the above chemical formula 1, R 1 is an alkyl group having 6 to 8 carbon atoms, and R 2 and R 3 Each independently represents hydrogen or an alkyl group having 2 to 6 carbon atoms, and R 2 and R 3 All of these may not be hydrogen.

[0069] According to one embodiment of the present invention, the lanthanide rare earth element compound is Nd(2-ethyl hexanoate)3 (neodymium versatate), Nd(2,2-dimethyl decanoate)3, Nd(2,2-diethyl decanoate)3, Nd(2,2-dipropyl decanoate)3, Nd(2,2-dibutyl decanoate)3, Nd(2,2-dihexyl decanoate)3, Nd(2,2-dioctyl decanoate)3, Nd(2-ethyl-2-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl Decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd(2-hexyl-2-octyl decanoate)3, Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl nonanoate)3, It may be at least one selected from the group consisting of Nd(2,2-dihexyl nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3, and Nd(2-ethyl-2-hexyl nonanoate)3.

[0070] According to one embodiment of the present invention, the neodymium compound includes a carboxylate ligand having an alkyl group of various lengths having 2 or more carbon atoms as a substituent at the α-position, thereby inducing a steric change around the neodymium central metal, thereby preventing aggregation between compounds, and thus has the effect of suppressing oligomerization during polymerization of a conjugated diene polymer using the catalyst composition. In addition, such a neodymium compound has high solubility in a solvent, and has the effect of reducing the proportion of neodymium located in the central portion, which is difficult to convert to a catalytically active species, thereby increasing the conversion rate to a catalytically active species.

[0071] According to one embodiment of the present invention, the solubility of the neodymium compound may be about 60 parts by weight or more per 100 parts by weight of a non-polar solvent at room temperature (25°C). The solubility of the neodymium compound refers to the degree to which it dissolves clearly without any cloudiness, and by exhibiting such high solubility, it can exhibit excellent catalytic activity.

[0072] According to one embodiment of the present invention, the step (S10) may be carried out including a conjugated diene monomer. This is to form a pre-polymerized or premixed catalyst composition by pre-mixing the conjugated diene monomer used in the polymerization reaction of the conjugated diene polymer using the catalyst composition manufactured according to the present invention with the catalyst composition, thereby further improving the activity of the catalyst composition and stabilizing the active polymer produced. The "preforming" may mean that a small amount of a conjugated diene monomer such as 1,3-butadiene is added to the catalyst composition including a neodymium compound, an alkylating agent, and a halide, i.e., in order to reduce the possibility of generating active species of various catalyst compositions in the catalyst system, and pre-polymerization is performed within the catalyst composition system together with the addition of 1,3-butadiene. Additionally, “premix” may mean a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

[0073] According to one embodiment of the present invention, the conjugated diene monomer that can be introduced in the step (S10) may be 1,3-butadiene or derivatives thereof, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene, and may also be 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene.

[0074] According to one embodiment of the present invention, when the step (S10) is carried out by including a conjugated diene monomer, the conjugated diene monomer may be introduced in a molar ratio of 1 mol or more, 5 mol or more, 10 mol or more, 15 mol or more, or 20 mol or more per mol of the lanthanide series rare earth element compound, and may also be introduced in a molar ratio of 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.

[0075] According to one embodiment of the present invention, the step (S20) is a step for performing an alkylation reaction on a lanthanide series rare earth element compound, which may be performed by mixing and reacting a lanthanide series rare earth element compound that has been pretreated in a hydrogen bond, oligomer form, or a combination thereof in the step (S10) with an alkylating agent.

[0076] According to one embodiment of the present invention, the alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and may function as a cocatalyst. The alkylating agent may be an organometallic compound that is soluble in a polymerization solvent and contains a metal-carbon bond, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound.

[0077] According to one embodiment of the present invention, the alkylating agent may be an organoaluminum compound, and specific examples thereof include alkyl aluminum such as tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; Diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride (DIBAH), di-n-octyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenylisopropyl aluminum hydride, phenyl-n-butyl aluminum hydride, phenylisobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolylisopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolylisobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzylethyl aluminum hydride, benzyl-n-propyl aluminum Dihydrocarbylaluminum hydrides such as hydride, benzylisopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzylisobutyl aluminum hydride or benzyl-n-octyl aluminum hydride; hydrocarbylaluminum dihydrides such as ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride or n-octyl aluminum dihydride;

[0078] According to one embodiment of the present invention, the alkylating agent may be preferably an alkyl aluminum compound from the viewpoint of controlling the catalytic reaction and side reactions according to the lanthanide rare earth element compound pretreated in the form of hydrogen bonds, oligomers, or a combination thereof in the step (S10). As a specific example, the alkylating agent may be an alkyl aluminum compound represented by the following chemical formula 2.

[0079] [Chemical Formula 2]

[0080] AlR 4 R 5 R 6

[0081] In the above chemical formula 2, R 4 Inland R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 4 Inland R 6 Not all of these are hydrogen, and do not include tri-n-hexyl aluminum and tri-n-octyl aluminum. As a specific example, in the above chemical formula 2, R 4 Inland R 6 are each independently hydrogen or an alkyl group having 3 to 8 carbon atoms, and R 4 Inland R 6 Not all of these are hydrogen, and do not include tri-n-hexyl aluminum and tri-n-octyl aluminum. As a more specific example, in the above formula 2, R 4 Inland R 6 are each independently hydrogen or an alkyl group having 3 to 5 carbon atoms, and R 4 Inland R 6 Not all of these are hydrogen, and do not include tri-n-hexyl aluminum and tri-n-octyl aluminum.

[0082] According to one embodiment of the present invention, the alkylating agent may be a dialkyl aluminum hydride from the viewpoint of controlling the catalytic reaction and side reaction according to the lanthanide rare earth element compound pretreated in the step (S10) in the form of a hydrogen bond, an oligomer, or a combination thereof, and the type of the dialkyl aluminum hydride is as described above. As a specific example, the alkylating agent may be diisobutyl aluminum hydride.

[0083] According to one embodiment of the present invention, the alkylating agent may include two or more alkyl aluminum compounds. As a specific example, the alkylating agent may include two or more selected from the group consisting of dialkyl aluminum hydride and trialkyl aluminum. As a more specific example, the alkylating agent may include one or more dialkyl aluminum hydride and one or more trialkyl aluminum, and as a still more specific example, the alkylating agent may include diisobutyl aluminum hydride and triisobutyl aluminum.

[0084] According to one embodiment of the present invention, the step (S20) may be carried out by introducing an alkylating agent in a molar ratio of 1 mol or more, 2 mol or more, 3 mol or more, 4 mol or more, 5 mol or more, 6 mol or more, 7 mol or more, 8 mol or more, 9 mol or more, 10 mol or more, 11 mol or more, 12 mol or more, 13 mol or more, 14 mol or more, or 15 mol or more, based on 1 mol of the lanthanide rare earth element compound pretreated in the hydrogen bond, oligomer form, or a combination thereof in the step (S10), and also, 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, or 15 mol or less. It can be implemented by inputting it in molar ratio.

[0085] According to one embodiment of the present invention, the step (S20) may be performed at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, and may also be performed 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.

[0086] According to one embodiment of the present invention, the step (S20) may be performed for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more, and may also be performed for 2 hours or less, 1 hour and 30 minutes or less, 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0087] According to one embodiment of the present invention, the step (S20) can further improve the catalytic activity by controlling the molar ratio, reaction temperature, and reaction time between the lanthanide rare earth element compound and the alkylating agent, which are pretreated in the hydrogen bond, oligomer form, or a combination thereof in the step (S10).

[0088] According to one embodiment of the present invention, the step (S20) may be carried out including a conjugated diene monomer for the same purpose as the step (S10). In this case, when the step (S20) is carried out including a conjugated diene monomer, it may be carried out separately from the step (S10) or simultaneously with the conjugated diene monomer.

[0089] According to one embodiment of the present invention, when the step (S20) is carried out by including a conjugated diene monomer, the conjugated diene monomer may be carried out by introducing the conjugated diene monomer in a molar ratio of 1 mol or more, 5 mol or more, 10 mol or more, 15 mol or more, or 20 mol or more per mol of the lanthanide rare earth element compound pretreated in the form of a hydrogen bond, an oligomer, or a combination thereof in the step (S10), and may also be introduced in a molar ratio of 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.

[0090] According to one embodiment of the present invention, the step (S20) may be performed continuously in a plurality of reactors connected in series. In this case, since the alkylation reaction is performed in the plurality of reactors connected in series, the alkylation reaction can sufficiently progress, thereby further improving the activity of the catalyst composition. At this time, the alkylating agent may be injected only into the first reactor among the plurality of reactors connected in series for performing the step (S20), and may also be injected in a divided manner into the plurality of reactors connected in series for performing the step (S20). When the alkylating agent is injected in a divided manner into the plurality of reactors, the reactor into which the alkylating agent is injected may be selected as needed. In addition, the alkylating agent injected in a divided manner into the plurality of reactors connected in series may be of the same or different types.

[0091] According to one embodiment of the present invention, the flow of reactants in the plurality of reactors connected in series in the step (S20) can be independently performed in a top-down manner or a bottom-up manner.

[0092] According to one embodiment of the present invention, at least one of the plurality of serially connected reactors in step (S20) may comprise a tubular reactor equipped with a line mixer. In this case, by retaining the reactants within the tubular reactor connected between the serially connected reactors, continuous mixing of the reactants is possible, thereby allowing the alkylation reaction to proceed more sufficiently.

[0093] According to one embodiment of the present invention, the step (S30) is a step for performing a halogenation reaction on the alkylated lanthanide rare earth element compound in the step (S20), and can be performed by mixing and reacting the alkylated lanthanide rare earth element compound in the step (S20) with a halide.

[0094] According to one embodiment of the present invention, the halide may be a halogen compound, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometallic halide.

[0095] According to one embodiment of the present invention, the halogen group may be fluorine, chlorine, bromine or iodine.

[0096] According to one embodiment of the present invention, the halogen compound may be iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, or iodine trifluoride.

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

[0098] According to one embodiment of the present invention, the organic halide is t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called 'iodoform'), tetraiodomethane, 1-iodopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called 'neopentyl iodide'), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide or methyl iodoformate.

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

[0100] According to one embodiment of the present invention, the metal halide may be tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

[0101] According to one embodiment of the present invention, the organometallic halide may be an alkyl aluminum halide or an alkyl aluminum sesquihalide.As a specific example, the organometallic halide is dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, methyl aluminum difluoride, ethyl aluminum difluoride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride (EASC), isobutyl aluminum sesquichloride, methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride, trimethyl tin chloride, trimethyl tin bromide, triethyl tin chloride, triethyl tin bromide, di-t-butyl tin dichloride, Di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide, methyl magnesium iodide, dimethyl aluminum iodide, diethyl aluminum iodide, di-n-butyl aluminum iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, methyl aluminum sesquiiodide, ethyl aluminum sesquiiodide, isobutyl aluminum sesquiiodide, ethyl magnesium iodide, n-butyl magnesium iodide, isobutyl magnesium iodide, phenyl magnesium iodide, benzyl magnesium iodide, trimethyl tin It may be iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin diiodide or di-t-butyltin diiodide.

[0102] According to one embodiment of the present invention, the halide may be at least one selected from the group consisting of an alkyl aluminum halide represented by the following chemical formula 3 and an alkyl aluminum sesquihalide represented by the following chemical formula 4, from the viewpoint of improving catalytic activity and thus reactivity.

[0103] [Chemical Formula 3]

[0104] AlR 7 R 8 R 9

[0105] In the above chemical formula 3, R 7 Inland R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R 7 Inland R 9 Not all of them may be halogen groups. As a specific example, in the above chemical formula 3, R 7 Inland R 9 are each independently a halogen group or an alkyl group having 1 to 6 carbon atoms, and R 7 Inland R 9 Not all of them may be halogen groups. As a more specific example, in the above chemical formula 3, R 7 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms, and R 9 may be a halogen group.

[0106] [Chemical Formula 4]

[0107]

[0108] In the above chemical formula 4, R 10 Inland R 12 Each of may independently be an alkyl group having 1 to 12 carbon atoms, and X1 to X3 may each independently be a halogen group. As a specific example, in the chemical formula 4, R 10 Inland R 12 Each of may independently be an alkyl group having 1 to 6 carbon atoms. As a more specific example, in the chemical formula 4, R10 Inland R 12 Each may independently be an alkyl group having 1 to 4 carbon atoms.

[0109] According to one embodiment of the present invention, the halide may be at least one selected from the group consisting of dialkyl aluminum halides and alkyl aluminum sesquihalides from the viewpoint of controlling the catalytic reaction and side reaction according to the lanthanide rare earth element compound pretreated in the form of hydrogen bonds, oligomers, or a combination thereof in the step (S10), and the types of the dialkyl aluminum halides and alkyl aluminum sesquihalides are as described above. As a specific example, the dialkyl aluminum halide may be diethyl aluminum chloride, and the alkyl aluminum sesquihalide may be ethyl aluminum sesquichloride.

[0110] According to one embodiment of the present invention, the step (S30) may be carried out by introducing a halide in a molar ratio of 0.1 mol or more, 0.5 mol or more, 1.0 mol or more, 1.5 mol or more, 2.0 mol or more, 2.5 mol or more, or 3.0 mol or more per mol of the lanthanide rare earth element compound pretreated in the form of a hydrogen bond, an oligomer, or a combination thereof in the step (S10), and may also be carried out by introducing a halide in a molar ratio of 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.

[0111] According to one embodiment of the present invention, the step (S30) may be performed at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, and may also be performed 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 one embodiment of the present invention, the step (S30) may be performed for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more, and may also be performed for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0113] According to one embodiment of the present invention, the step (S30) can further improve the catalytic activity by controlling the molar ratio, reaction temperature, and reaction time between the lanthanide rare earth element compound and the halide, which are pretreated in the hydrogen bond, oligomer form, or a combination thereof in the step (S10).

[0114] According to one embodiment of the present invention, steps (S10) to (S30) may be performed in an organic solvent. The organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition. As a specific example, the organic solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms, such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclopentane, cyclohexane, methylcyclopentane or methylcyclohexane; a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether or petroleum spirits, or kerosene; Or it may be an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, etc. As a more specific example, the organic solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, and preferably n-hexane, cyclohexane, or a mixture thereof.

[0115] According to one embodiment of the present invention, steps (S10), (S20), and (S30) may be performed in individual reactors connected in series, respectively. Therefore, at least three reactors are required to produce a catalyst according to the method for producing a catalyst composition. In addition, when step (S20) is performed sequentially in multiple reactors connected in series, at least one reactor for performing step (S10), two or more reactors for performing step (S20), and one or more reactors for performing step (S30), a total of four or more reactors, are required to produce a catalyst according to the method for producing a catalyst composition.

[0116] According to one embodiment of the present invention, steps (S10), (S20), and (S30) may be performed sequentially. That is, steps (S10), (S20), and (S30) may be performed sequentially in individual reactors connected in series, and in this case, the productivity of the catalyst composition and the conjugated diene polymer using the same may be improved, and more uniform quality may be secured.

[0117] According to one embodiment of the present invention, the flow of reactants in individual reactors each connected in series can be independently performed in a top-down manner or a bottom-up manner.

[0118] According to one embodiment of the present invention, the entire steps of the method for preparing a catalyst composition including steps (S10) to (S30) may be performed at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, and may also be performed 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.

[0119] According to one embodiment of the present invention, the entire steps of the catalyst composition preparation method including steps (S10) to (S30) may be performed for 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, or 70 minutes or more, and may also be performed for 2 hours or less, 1 hour and 50 minutes or less, 1 hour and 40 minutes or less, 1 hour and 30 minutes or less, 1 hour and 20 minutes or less, or 1 hour and 10 minutes or less.

[0120]

[0121] Method for producing conjugated diene polymers

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

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

[0124] According to one embodiment of the present invention, the conjugated diene monomer that can be introduced in the step (S100) may be at least one selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene.

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

[0126] According to one embodiment of the present invention, the catalyst composition may be a catalyst composition manufactured by the catalyst composition manufacturing method described above, and the catalyst composition may be used in an amount such that the neodymium compound is 0.03 mmol or more, 0.04 mmol or more, 0.05 mmol or more, or 0.06 mmol or more, based on a total of 100 g of the conjugated diene monomer, and may also be used in an amount such that the neodymium compound is 0.15 mmol or less, 0.14 mmol or less, 0.13 mmol or less, 0.12 mmol or less, 0.11 mmol or less, 0.10 mmol or less, 0.09 mmol or less, or 0.08 mmol or less.

[0127] According to one embodiment of the present invention, the polymerization in step (S100) may be performed as a continuous polymerization in a polymerization reactor comprising at least two reactors, or may be performed in a batch reactor. In addition, the polymerization may be a temperature-elevated polymerization, an isothermal polymerization, or a constant-temperature polymerization (adiabatic polymerization).

[0128] According to one embodiment of the present invention, the isothermal polymerization means polymerizing with the heat of reaction itself without arbitrarily applying heat after introducing the catalyst composition, the temperature-increasing polymerization means increasing the temperature by arbitrarily applying heat after introducing the catalyst composition, and the isothermal polymerization means increasing the temperature by applying heat or removing heat after introducing the catalyst composition to keep the temperature of the reactants constant.

[0129] According to one embodiment of the present invention, the polymerization in the step (S100) may be carried out using coordination anionic polymerization, and the polymerization environment may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and a specific example may be solution polymerization.

[0130] According to one embodiment of the present invention, the polymerization in the step (S100) can be carried out at a temperature of -20°C or higher, -10°C or higher, 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher, and can also be carried out at a temperature of 200°C or lower, 150°C or lower, 120°C or lower, or 90°C or lower, and within this range, the polymerization reaction can be smoothly controlled while securing the cis-1,4 bond content of the produced conjugated diene polymer.

[0131] According to one embodiment of the present invention, the polymerization in step (S100) may be performed for 15 minutes or more, 20 minutes or more, 30 minutes or more, 40 minutes or more, 50 minutes or more, or 1 hour or more, and may also be performed for 3 hours or less, 2 hours and 30 minutes or less, or 2 hours or less.

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

[0133] According to one embodiment of the present invention, the method may include a step (S200) of reacting the active polymer with a modifier. The modifier may be a known modifier that can be used when producing a conjugated diene polymer using a catalyst composition containing a lanthanide series rare earth element compound.

[0134] According to one embodiment of the present invention, the method for producing the conjugated diene polymer may further include a step of terminating the polymerization by further using an additive, such as a reaction terminator for completing the polymerization reaction, such as polyoxyethylene glycol phosphate, or an antioxidant, such as 2,6-di-t-butylparacresol, after producing the active polymer. In addition, an additive that facilitates solution polymerization, such as a chelating agent, a dispersing agent, a pH regulator, a deoxidizer, or an oxygen scavenger, may be optionally further used together with the reaction terminator.

[0135]

[0136] conjugated diene polymer

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

[0138] According to one embodiment of the present invention, the conjugated diene polymer may be manufactured by the conjugated diene polymer manufacturing method. That is, the conjugated diene polymer may be polymerized in the presence of a catalyst composition manufactured by the catalyst composition manufacturing method described above.

[0139] According to one embodiment of the present invention, the conjugated diene polymer may include a conjugated diene monomer unit. The conjugated diene monomer unit refers to a repeating unit formed by polymerization of a conjugated diene monomer.

[0140] According to one embodiment of the present invention, the conjugated diene polymer may comprise 80 wt% or more, 85 wt% or more, 90 wt% or more, 95 wt% or more, or 100 wt% of a 1,3-butadiene monomer unit, and optionally 20 wt% or less, 15 wt% or less, 10 wt% or less, or 5 wt% or less of other conjugated diene monomer units copolymerizable with the 1,3-butadiene monomer, and within this range, a decrease in the cis-1,4 bond content in the conjugated diene polymer may be prevented. The above 1,3-butadiene monomer may be 1,3-butadiene or a derivative thereof, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene, and other conjugated diene monomers copolymerizable with the above 1,3-butadiene may be 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene.

[0141] According to one embodiment of the present invention, the conjugated diene polymer may be a conjugated diene polymer catalyzed by a catalyst composition comprising a lanthanide series rare earth element compound. That is, the conjugated diene polymer may be a conjugated diene polymer including an organometallic moiety activated by a catalyst composition comprising a neodymium compound.

[0142] According to one embodiment of the present invention, the conjugated diene polymer has a weight average molecular weight (Mw) of 1.0 Х 10 5 g / mol or more, 2.0 Х 10 5 g / mol or more, 3.0 Х 10 5 g / mol or more, 4.0 Х 10 5 g / mol or more, 5.0 Х 10 5 g / mol or more, 6.0 Х 10 5 g / mol or more, 7.0 Х 10 5 g / mol or more, 8.0 Х 10 5g / mol or more or 9.0 Х 10 5 g / mol or more, and also 1.0 Х 10 6 g / mol or less, 9.0 Х 10 5 g / mol or less, 8.0 Х 10 5 g / mol or less, 7.0 Х 10 5 g / mol or less, 6.0 Х 10 5 g / mol or less, 5.0 Х 10 5 g / mol or less, 4.0 Х 10 5 g / mol or less, or 3.0 Х 10 5 g / mol or less. In addition, the conjugated diene polymer has a number average molecular weight (Mn) of 1.0 Х 10 5 g / mol or more, 2.0 Х 10 5 g / mol or more, 3.0 Х 10 5 g / mol or more, 4.0 Х 10 5 g / mol or more, or 5.0 Х 10 5 g / mol or more, and also 6.0 Х 10 5 g / mol or less, 5.0 Х 10 5 g / mol or less, 4.0 Х 10 5 g / mol or less, 3.0 Х 10 5 g / mol or less, 2.0Х10 5 g / mol or less, or 1.0 Х 10 5 It may be less than g / mol. Within this range, when applied to a rubber composition, the tensile properties are excellent, and the processability is excellent, so the workability of the rubber composition is improved, making it easy to mix, and the mechanical properties and property balance of the rubber composition are excellent.

[0143] According to one embodiment of the present invention, the conjugated diene polymer may have a molecular weight distribution (Mw / Mn) of 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 may also have a molecular weight distribution of 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) to the number average molecular weight (Mn). Here, the number average molecular weight (Mn) is a common average of individual polymer molecular weights calculated by measuring the molecular weights of n polymer chains, obtaining the sum of these molecular weights, and dividing the result by n, and the weight average molecular weight (Mw) represents the molecular weight distribution of the polymer composition. All molecular weight averages can be expressed in grams per mole (g / mol). Additionally, the above weight average molecular weight and number average molecular weight may each mean a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0144] According to one embodiment of the present invention, when the conjugated diene polymer simultaneously satisfies the conditions of weight average molecular weight (Mw) and number average molecular weight along with the molecular weight distribution, when applied to a rubber composition, the rubber composition has excellent tensile properties, viscoelasticity, and processability, and has an excellent balance of physical properties therebetween.

[0145] According to one embodiment of the present invention, the conjugated diene polymer may have a cis-1,4 bond content of 97.0 wt% or more, 97.1 wt% or more, 97.2 wt% or more, 97.3 wt% or more, 97.4 wt% or more, 97.5 wt% or more, 97.6 wt% or more, 97.7 wt% or more, 97.8 wt% or more, 97.9 wt% or more, 98.0 wt% or more, or 98.1 wt% or more, and may also have a cis-1,4 bond content of 100.0 wt% or less, 99.5 wt% or less, or 99.0 wt% or less.

[0146] According to one embodiment of the present invention, the conjugated diene polymer may have a Mooney viscosity (ML1+4, @100°C) of 30 or more, 35 or more, 40 or more, 41 or more, 42 or more, 43 or more, 44 or more, or 45 or more, and may also have a Mooney viscosity of 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, or 49 or less.

[0147]

[0148] rubber composition

[0149] The present invention provides a rubber composition.

[0150] According to one embodiment of the present invention, the rubber composition may include the conjugated diene polymer. As a specific example, the rubber composition may include the conjugated diene polymer in an amount of 0.1 wt% or more, 10 wt% or more, or 20 wt% or more, and further, may include the conjugated diene polymer in an amount of 100 wt% or less, 95 wt% or less, or 90 wt% or less, and within this range, the wear resistance and crack resistance of a molded article, for example, a tire, manufactured using the rubber composition can be sufficiently secured.

[0151] According to one embodiment of the present invention, the rubber composition may further include other rubber components as needed in addition to the conjugated diene polymer. In this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, the rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the conjugated diene copolymer.

[0152] According to one embodiment of the present invention, the rubber component may be natural rubber or synthetic rubber, and for example, the rubber component may be natural rubber (NR) including cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or purified natural rubbers; It may be a synthetic rubber such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and any one or a mixture of two or more of these may be used.

[0153] According to one embodiment of the present invention, the rubber composition may contain a filler in an amount of 20 parts by weight or more and 90 parts by weight or less, based on 100 parts by weight of the conjugated diene polymer. The filler may be a silica-based filler, a carbon black-based filler, or a combination thereof. As a specific example, the filler may be a carbon black-based filler.

[0154] According to one embodiment of the present invention, the carbon black filler has a nitrogen adsorption surface area (N2SA, measured in accordance with JIS K 6217-2:2001) of 20 m 2 / g to 250 m 2 / g, and within this range, the rubber composition can have excellent processability while sufficiently securing reinforcing performance by the filler. In addition, the carbon black-based filler can have a dibutyl phthalate absorption (DBP) of 80 cc / 100g to 200 cc / 100g, and within this range, the rubber composition can have excellent processability while sufficiently securing reinforcing performance by the filler.

[0155] According to one embodiment of the present invention, the silica-based filler may be wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. As a specific example, the silica-based filler may be wet silica, which has the most remarkable effect of improving fracture characteristics and achieving wet grip. In addition, the silica-based filler may have a nitrogen adsorption surface area per gram (N2SA) of 120 m 2 / g to 180 m 2 / g, and the CTAB (cetyl trimethyl ammonium bromide) adsorption surface area is 100 m 2 / g to 200 m 2 / g, and within this range, the processability of the rubber composition can be excellent while sufficiently securing reinforcing performance by the filler.

[0156] According to one embodiment of the present invention, when a silica-based filler is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation properties. The above silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-Triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-Trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-Triethoxysilylpropylbenzolyltetrasulfide, 3-Triethoxysilylpropylmethacrylate monosulfide, 3-Trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-Mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. As a specific example, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide when considering the effect of improving reinforcing properties.

[0157] According to one embodiment of the present invention, the rubber composition may be sulfur-crosslinkable and thus may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, and within this range, the required elastic modulus and strength of the vulcanized rubber composition can be secured, while at the same time ensuring low fuel consumption.

[0158] According to one embodiment of the present invention, the rubber composition may further include, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

[0159] According to one embodiment of the present invention, the vulcanization accelerator is not particularly limited, and specifically, thiazole compounds such as M(2-mercaptobenzothiazole), DM(dibenzothiazyl disulfide), CZ(N-cyclohexyl-2-benzothiazylsulfenamide), or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator can be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

[0160] According to one embodiment of the present invention, the process oil acts as a softener in the rubber composition, and specific examples thereof may be paraffinic, naphthenic, or aromatic compounds. More specifically, when considering tensile strength and wear resistance, an aromatic process oil may be used, and when considering hysteresis loss and low-temperature characteristics, a naphthenic or paraffinic process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, a decrease in tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber may be prevented.

[0161] According to one embodiment of the present invention, the anti-aging agent may be N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0162] According to one embodiment of the present invention, the rubber composition can be obtained by mixing using a mixer such as a Banbury mixer, a roll mixer, or an internal mixer according to the above compounding prescription, and further, a rubber composition having low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding processing.

[0163] According to one embodiment of the present invention, the rubber composition may be useful in the manufacture of various components of a tire, such as a tire tread, undertread, sidewall, carcass coating rubber, belt coating rubber, bead filler, squeegee, or bead coating rubber, or various industrial rubber products, such as an anti-vibration rubber, a belt conveyor, or a hose. As a specific example, a molded product manufactured using the rubber composition may include a tire or a tire tread.

[0164]

[0165] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0166]

[0167] Example

[0168] Example 1

[0169] Three pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.16 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.05 kg / hr, and a tri-n-octyl aluminum solution diluted with a concentration of 25 wt% in n-hexane was continuously injected in an amount such that tri-n-octyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted with n-hexane to a concentration of 50 wt% was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted with n-hexane to a concentration of 30 wt% was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0170]

[0171] Example 2

[0172] Three pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.16 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.05 kg / hr, and a tri-n-octyl aluminum solution diluted with a concentration of 25 wt% in n-hexane was continuously injected in an amount such that tri-n-octyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a triisobutyl aluminum solution diluted with n-hexane to a concentration of 50 wt% was continuously injected into the second reactor in an amount such that triisobutyl aluminum was 30 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted with n-hexane to a concentration of 30 wt% was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0173]

[0174] Example 3

[0175] Three pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.12 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.03 kg / hr, and a tri-n-octyl aluminum solution diluted with a concentration of 25 wt% in n-hexane was continuously injected in an amount such that 20 mol of tri-n-octyl aluminum was used per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted with n-hexane to a concentration of 50 wt% was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted with n-hexane to a concentration of 30 wt% was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0176]

[0177] Example 4

[0178] Three pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.16 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.05 kg / hr, and a tri-n-octyl aluminum solution diluted with a concentration of 25 wt% in n-hexane was continuously injected in an amount such that tri-n-octyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted with n-hexane to a concentration of 50 wt% was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 mol per 1 mol of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a solution of ethyl aluminum sesquichloride diluted with n-hexane to a concentration of 10 wt% was continuously injected into the third reactor in an amount such that ethyl aluminum sesquichloride was 1.5 mol per 1 mol of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was aliquoted into a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0179]

[0180] Example 5

[0181] Three pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.16 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.05 kg / hr, and a tri-n-octyl aluminum solution diluted with a concentration of 25 wt% in n-hexane was continuously injected in an amount such that tri-n-octyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted to a concentration of 50 wt% in n-hexane was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 20 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted to a concentration of 30 wt% in n-hexane was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0182]

[0183] Example 6

[0184] Four pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 15 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.08 kg / hr, and at the same time, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-octyl aluminum solution diluted with a concentration of 25 wt% in n-hexane was continuously injected in an amount such that tri-n-octyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted to a concentration of 10 wt% in n-hexane was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 15 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor. The temperature of the third reactor was operated at 10 ℃, and after 15 minutes of continuous injection, the reactant in the third reactor was transferred to the fourth reactor. A diethyl aluminum chloride solution diluted to a concentration of 30 wt% in n-hexane was continuously injected into the fourth reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the fourth reactor was operated at -5 ℃, and after 15 minutes of continuous injection, the prepared catalyst composition was aliquoted into a pressure vessel prepared in a nitrogen atmosphere and stored at a temperature below 0 ℃.

[0185]

[0186] Example 7

[0187] Four pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. At this time, the third and fourth reactors were connected using a pipe equipped with a line mixer. Each reactor was maintained in a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 15 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.08 kg / hr, and at the same time, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-octyl aluminum solution diluted with a concentration of 25 wt% in n-hexane was continuously injected in an amount such that tri-n-octyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted to a concentration of 10 wt% in n-hexane was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 15 minutes of continuous injection, the reactant from the second reactor was transferred to the third reactor. The temperature of the third reactor was operated at 0 ℃, and after 15 minutes of continuous injection, the reactant from the third reactor was kept at 0 ℃ for 15 minutes in a pipe equipped with a line mixer and then transferred to the fourth reactor. A diethyl aluminum chloride solution diluted to a concentration of 30 wt% in n-hexane was continuously injected into the fourth reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the fourth reactor was operated at -5 ℃, and after 15 minutes of continuous injection, the prepared catalyst composition was aliquoted into a pressure vessel prepared in a nitrogen atmosphere and stored at a temperature below 0 ℃.

[0188]

[0189] Example 8

[0190] Three pressure reactors, each having a volume of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.24 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-hexyl aluminum solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that tri-n-hexyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted with n-hexane to a concentration of 50 wt% was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted with n-hexane to a concentration of 30 wt% was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0191]

[0192] Example 9

[0193] Three pressure reactors, each having a volume of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.20 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.06 kg / hr, and a tri-n-hexyl aluminum solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that tri-n-hexyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a triisobutyl aluminum solution diluted with n-hexane to a concentration of 50 wt% was continuously injected into the second reactor in an amount such that triisobutyl aluminum was 30 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted with n-hexane to a concentration of 30 wt% was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0194]

[0195] Example 10

[0196] Three pressure reactors, each with a volume of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.20 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.06 kg / hr, and a tri-n-hexyl aluminum solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that tri-n-hexyl aluminum was 20 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted with n-hexane to a concentration of 50 wt% was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted with n-hexane to a concentration of 30 wt% was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0197]

[0198] Example 11

[0199] Three pressure reactors, each having a volume of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.24 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-hexyl aluminum solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that tri-n-hexyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted to a concentration of 50 wt% in n-hexane was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a solution of ethyl aluminum sesquichloride diluted to a concentration of 50 wt% in n-hexane was continuously injected into the third reactor in an amount such that ethyl aluminum sesquichloride was 1.5 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0200]

[0201] Example 12

[0202] Three pressure reactors, each having a volume of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.24 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.07 kg / hr, and a tri-n-hexyl aluminum solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that tri-n-hexyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted to a concentration of 50 wt% in n-hexane was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 20 ℃, and after 30 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor, and a diethyl aluminum chloride solution diluted to a concentration of 30 wt% in n-hexane was continuously injected into the third reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the third reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0203]

[0204] Example 13

[0205] Four pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 10 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.14 kg / hr, and simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.08 kg / hr, and a tri-n-hexyl aluminum solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that tri-n-hexyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted to a concentration of 10 wt% in n-hexane was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 15 minutes of continuous injection, the reactant in the second reactor was transferred to the third reactor. The temperature of the third reactor was operated at 10 ℃, and after 15 minutes of continuous injection, the reactant in the third reactor was transferred to the fourth reactor. A diethyl aluminum chloride solution diluted to a concentration of 30 wt% in n-hexane was continuously injected into the fourth reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the fourth reactor was operated at -5 ℃, and after 15 minutes of continuous injection, the prepared catalyst composition was aliquoted into a pressure vessel prepared in a nitrogen atmosphere and stored at a temperature below 0 ℃.

[0206]

[0207] Example 14

[0208] Four pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. At this time, the third and fourth reactors were connected using a pipe equipped with a line mixer. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 10 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.14 kg / hr, and at the same time, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.08 kg / hr, and a tri-n-hexyl aluminum solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that tri-n-hexyl aluminum was 10 mol per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the mixture mixed in the first reactor was transferred to the second reactor, and a diisobutyl aluminum hydride solution diluted to a concentration of 10 wt% in n-hexane was continuously injected into the second reactor in an amount such that diisobutyl aluminum hydride was 15 moles per 1 mole of neodymium. The temperature of the second reactor was operated at 10 ℃, and after 15 minutes of continuous injection, the reactant from the second reactor was transferred to the third reactor. The temperature of the third reactor was operated at 0 ℃, and after 15 minutes of continuous injection, the reactant from the third reactor was kept at 0 ℃ for 15 minutes in a pipe equipped with a line mixer and then transferred to the fourth reactor. A diethyl aluminum chloride solution diluted to a concentration of 30 wt% in n-hexane was continuously injected into the fourth reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the fourth reactor was operated at -5 ℃, and after 15 minutes of continuous injection, the prepared catalyst composition was aliquoted into a pressure vessel prepared in a nitrogen atmosphere and stored at a temperature below 0 ℃.

[0209]

[0210] Comparative Example 1

[0211] Two pressure reactors, each with a capacity of 300 ml and equipped with a jacket and a stirrer, were connected in series and used as a continuous catalyst production reactor. Each reactor was maintained under a nitrogen atmosphere. A neodymium versatate solution diluted with a concentration of 5 wt% in n-hexane was continuously injected into the first reactor at a flow rate of 0.32 kg / hr. Simultaneously, 1,3-butadiene diluted with a concentration of 5 wt% in n-hexane was continuously injected at a flow rate of 0.09 kg / hr. A diisobutyl aluminum hydride solution diluted with a concentration of 50 wt% in n-hexane was continuously injected in an amount such that 15 mol of diisobutyl aluminum hydride was used per 1 mol of neodymium. The temperature of the first reactor was operated at 10 ℃, and after 30 minutes of continuous injection, the reactants of the first reactor were transferred to the second reactor, and a diethyl aluminum chloride solution diluted to a concentration of 30 wt% in n-hexane was continuously injected into the second reactor in an amount such that diethyl aluminum chloride was 3 moles per 1 mole of neodymium. The temperature of the second reactor was operated at -5 ℃, and after 30 minutes of continuous injection, the prepared catalyst composition was aliquoted into a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature of 0 ℃ or lower.

[0212]

[0213] Comparative Example 2

[0214] 2.1 g of 1,3-butadiene diluted in n-hexane to a concentration of 4.5 wt% was added to the reactor, and 0.6 g of neodymium versatate (Solvay) diluted in n-hexane to a concentration of 40 wt% was added. Then, diisobutyl aluminum hydride was added to the reactor at a temperature of 10°C in an amount of 15 moles of diisobutyl aluminum hydride per 1 mole of neodymium, and stirred for 30 minutes. Then, diethyl aluminum chloride was added to the reactor at a temperature of -5°C in an amount of 3 moles of diethyl aluminum chloride per 1 mole of neodymium, and stirred for 30 minutes, thereby preparing a catalyst composition.

[0215]

[0216] Comparative Example 3

[0217] 2.1 g of 1,3-butadiene diluted in n-hexane to a concentration of 4.5 wt% was added to the reactor, and 0.6 g of neodymium versatate (Solvay) diluted in n-hexane to a concentration of 40 wt% was added. Subsequently, triisobutyl aluminum was added to the reactor at a temperature of 10°C in an amount of 30 moles of triisobutyl aluminum per 1 mole of neodymium, and stirred for 30 minutes. Subsequently, diethyl aluminum chloride was added to the reactor at a temperature of -5°C in an amount of 3 moles of diethyl aluminum chloride per 1 mole of neodymium, and stirred for 30 minutes, thereby preparing a catalyst composition.

[0218]

[0219] Experimental example

[0220] Experimental Example 1: Preparation of conjugated diene polymer and evaluation of catalyst composition activity

[0221] After placing 500 g of 1,3-butadiene and 4.2 kg of n-hexane in a 20 L autoclave reactor, the internal temperature of the reactor was raised to 70 ℃. When the catalyst compositions prepared in Examples 1 to 14 were used in the reactor, diisobutyl aluminum hydride was added as a molecular weight regulator in an amount of 0.02 parts by weight relative to 100 parts by weight of 1,3-butadiene, and when the catalyst compositions prepared in Comparative Examples 1 to 3 were used, diisobutyl aluminum hydride was added as a molecular weight regulator in an amount of 0.05 parts by weight relative to 100 parts by weight of 1,3-butadiene, and after the catalyst compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were added, polymerization was performed, and when the polymerization conversion rate became 98% or more, an n-hexane solution containing 1.0 g of a polymerization terminator and a solution in which 30 wt% of an antioxidant Irganox 1520 (BASF) was dissolved in n-hexane were added to terminate the reaction, and the obtained polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water. A butadiene polymer was prepared by removing it.

[0222] When producing the above butadiene polymer, after the start of polymerization, a portion of the polymerization solution was taken after 25 minutes of reaction time, and the TSC (total solid contents, %) was measured, and the polymerization conversion rate was calculated according to the following mathematical formula 1. The polymerization conversion rate after 25 minutes of reaction time was measured for each catalyst composition of Examples 1 to 4 and Comparative Examples 1 to 3 to evaluate the activity of the catalyst composition, which is shown in Tables 1 to 3 below. The measured value of Comparative Example 2 was used as the reference value, and the activity of the catalyst composition of each Example and Comparative Example was indexed using the following mathematical formula 2.

[0223]

[0224] [Mathematical Formula 1]

[0225] Polymerization conversion (%) = TSC of sample (%) / Concentration of 1,3-butadiene added (wt%)

[0226] [Equation 2]

[0227] Active Index = (Measurement / Reference) Ⅹ 100

[0228]

[0229] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Activity (25 min polymerization conversion, %) 85838485808887 Activity index (%) 155151153155145160158

[0230]

[0231] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Activity (25 min polymerization conversion, %) 87848886828887 Activity index (%) 158153160156149160158

[0232]

[0233] Comparison Example 1 Comparison Example 2 Comparison Example 3 Activity (25-minute polymerization conversion rate, %) 545545 Activity index (%) 9810082

[0234]

[0235] As shown in Table 1 above, it was confirmed that the catalyst compositions manufactured in Examples 1 to 14 exhibited very high activity compared to the catalyst compositions manufactured in Comparative Examples 1 to 3.

[0236] On the other hand, in the case of Comparative Example 1, which did not perform a pretreatment step using tri-n-hexyl aluminum and tri-n-octyl aluminum for the lanthanide rare earth element compound according to the present invention, it was confirmed that the activity of the catalyst composition was reduced compared to Examples 1 to 14, and particularly, compared to Examples 1, 3 to 8 and 10 to 14 using the same alkylating agent and halide.

[0237] In addition, in the case of Comparative Example 2, in which the catalyst composition was manufactured using a batch reactor without performing a pretreatment step using tri-n-hexyl aluminum and tri-n-octyl aluminum for the lanthanide rare earth element compound according to the present invention, it was confirmed that the activity of the catalyst composition was reduced compared to Examples 1 to 14, especially compared to Examples 1, 3 to 8 and 10 to 14 using the same alkylating agent and halide.

[0238] In addition, in the case of Comparative Example 3, in which a catalyst composition was manufactured using a batch reactor without performing a pretreatment step using tri-n-hexyl aluminum and tri-n-octyl aluminum for a lanthanide rare earth element compound according to the present invention, even when the alkylating agent was changed to triisobutyl aluminum and used in excess, the alkylation reaction did not proceed sufficiently, and it was confirmed that the activity of the catalyst composition was reduced compared to Examples 1 to 14, and especially compared to Examples 2 and 9 using the same alkylating agent and halide.

[0239]

[0240] Experimental Example 2: Evaluation of the properties of conjugated diene polymers

[0241] For the conjugated diene polymers prepared in Experimental Example 1 using the catalyst compositions of Examples 1 to 14 and Comparative Examples 1 to 3, Mooney viscosity, molecular weight distribution, and cis-1,4 bond content were measured as follows, and are shown in Tables 4 to 6 below.

[0242]

[0243] * Mooney viscosity (ML1+4, @100℃): For each polymer, Mooney viscosity was measured at 100℃ with a large rotor (Monsanto MV2000E) and a rotor speed of 2±0.02 rpm. The sample was left at room temperature (23±3℃) for more than 30 minutes, and then 27±3 g was collected and filled into the die cavity. The platen was operated to apply torque while Mooney viscosity was measured.

[0244]

[0245] * Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (MWD): Each polymer was dissolved in tetrahydrofuran (THF) at 40°C for 30 minutes, then loaded onto a gel permeation chromatography (GPC) column and run. At this time, two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories were used in combination. In addition, all newly replaced columns were mixed-bed type columns, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

[0246]

[0247] * 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, the FT-IR transmittance spectrum of the carbon disulfide solution of the conjugated diene polymer prepared at a concentration of 5 mg / mL using carbon disulfide as a blank in the same cell was measured, and then the 1130 cm of the measured spectrum -1 The maximum peak value near (a, baseline) is 967 cm, indicating a trans-1,4 bond. -1 The minimum peak value near (b) is 911 cm, indicating vinyl bonding. -1The minimum peak value (c) near 736 cm, indicating a cis-1,4 bond. -1 Each content was obtained using the minimum peak value (d) in the vicinity.

[0248]

[0249] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Mooney viscosity (MU) 47 46 40 45 48 43 41 Molecular weight distribution 2.4 2.5 2.5 2.4 2.4 2.3 2.3 cis-1,4 bond content (wt%) 98.1 97.9 97.3 98.0 98.0 97.6 97.9

[0250]

[0251] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Mooney viscosity (MU) 45 46 41 44 49 40 42 Molecular weight distribution 2.5 2.6 2.4 2.4 2.3 2.3 cis-1,4 bond content (wt%) 98.0 97.8 97.4 97.8 97.7 97.6 98.0

[0252]

[0253] Comparison Example 1 Comparison Example 2 Comparison Example 3 Mooney viscosity (MU) 434548 Molecular weight distribution 2.9 2.9 3.1 cis-1,4 bond content (weight%) 97.6 97.5 97.1

[0254]

[0255] As shown in Tables 4 to 6 above, it was confirmed that the conjugated diene polymers manufactured using the catalyst compositions manufactured in Examples 1 to 14 exhibited appropriate levels of Mooney viscosity and molecular weight distribution, while securing a high level of cis-1,4 bond content.

[0256] On the other hand, it was confirmed that the conjugated diene polymers manufactured using the catalyst compositions manufactured in Comparative Examples 1 to 3 had a wider molecular weight distribution compared to Examples 1 to 14.

[0257]

[0258] Experimental Example 3: Evaluation of Rubber Composition Properties

[0259] Using the catalyst compositions of Examples 1 to 14 and Comparative Examples 1 to 3, a rubber composition and a rubber specimen were prepared using the conjugated diene polymer prepared in Experimental Example 1. Then, Mooney viscosity, wear resistance, tensile properties, and viscoelastic properties of the rubber composition were measured using the following methods, and the results are shown in Tables 7 to 9 below.

[0260]

[0261] <Manufacture of rubber composition and rubber specimen>

[0262] Using the catalyst compositions of Examples 1 to 14 and Comparative Examples 1 to 3, 70 parts by weight of carbon black, 22.5 parts by weight of process 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 with each of 100 parts by weight of the conjugated diene polymer manufactured in Experimental Example 1.

[0263] Thereafter, 2 parts by weight of sulfur, 2 parts by weight of a vulcanization accelerator (CZ), and 0.5 parts by weight of a vulcanization accelerator (DPG) were added to each of the above rubber compositions, and gently mixed at 50 rpm for 1 minute and 30 seconds at 50°C, and then a sheet-shaped vulcanized mixture was prepared using a 50°C roll, and the vulcanized mixture was vulcanized at 160°C for 25 minutes to prepare a rubber specimen.

[0264]

[0265] * Tensile properties: Each rubber composition manufactured above was vulcanized at 150°C for t90 minutes, and the modulus at 300% elongation of the vulcanized product (M-300%, kg·f / cm) was measured according to ASTM D412. 2 ) was measured. The measured value of Comparative Example 2 was used as the reference value, and the 300% modulus of each example and comparative example was indexed using the following mathematical formula 3.

[0266] [Equation 3]

[0267] M-300% Index = (Measured value / Reference value) Ⅹ 100

[0268]

[0269] * Viscoelastic properties: Using DMTS 500N from Gabo, Germany, the viscoelastic coefficient (Tanδ) was measured at a frequency of 10 Hz, a prestrain of 3%, and a dynamic strain of 3% at -60°C to 60°C. The Tanδ value at 0°C represents road resistance, and the Tanδ value at 60°C represents rolling resistance characteristics (fuel efficiency). The measured values ​​of Comparative Example 2 were used as reference values, and the viscoelastic properties of each Example and Comparative Example were indexed using the following mathematical equation 4.

[0270] [Equation 4]

[0271] Tan δ 60 ℃ Index = (reference value / measured value) Ⅹ 100

[0272]

[0273] * Abrasion resistance: For each rubber specimen manufactured above, a DIN abrasion test was performed in accordance with ASTM D5963, and the results were expressed as DIN wt loss index (loss volume index: ARIA (Abrasion resistance index, Method A)). The measured value of Comparative Example 2 was used as the reference value, and the abrasion resistance of each example and comparative example was indexed using the following mathematical formula 5.

[0274] [Equation 5]

[0275] Wear Index = (Reference value / Measured value) Ⅹ 100

[0276]

[0277] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Tensile properties M-300% (kg·f / cm 2)90888688879088M-300% Index (%)113110108110109113110Viscoelastic propertiesTan δ 60 ℃0.1610.1640.1620.1600.1590.1580.160Tan δ 60 ℃ index (%)106104106107108108107Wear resistanceWear amount (mg)19.619.920.020.220.419.519.7Wear amount index (%)110108108106105110109

[0278]

[0279] Classification Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Tensile properties M-300% (kg·f / cm 2 )89908887858887M-300% Index (%)111113110109106110109Viscoelastic propertiesTan δ 60 ℃0.1600.1630.1610.1630.1590.1610.160Tan δ 60 ℃ index(%)107105106105108106107Wear resistanceWear amount (mg)20.019.820.220.821.019.819.5Wear amount index (%)108109106103102109110

[0280]

[0281] Comparison Example 1 Comparison Example 2 Comparison Example 3 Tensile properties M-300% (kg·f / cm 2 )798079M-300% Index (%)9910099Viscoelastic propertiesTan δ 60 ℃0.1740.1710.175Tan δ 60 ℃ index (%)9810098Wear resistanceWear amount (mg)22.121.522.1Wear amount index (%)9710097

[0282]

[0283] As shown in Tables 7 to 9 above, it was confirmed that the rubber compositions manufactured including the conjugated diene polymer manufactured using the catalyst compositions manufactured in Examples 1 to 4 had improved tensile properties, viscoelastic properties, and wear resistance compared to the rubber compositions manufactured including the conjugated diene polymer manufactured using the catalyst compositions manufactured in Comparative Examples 1 to 3.

[0284] On the other hand, it was confirmed that the rubber compositions manufactured including the conjugated diene polymer manufactured using the catalyst compositions manufactured in Comparative Examples 1 and 3 had lower tensile properties, viscoelastic properties, and wear resistance compared to the rubber compositions manufactured including the conjugated diene polymer manufactured using the catalyst composition manufactured in Comparative Example 2.

[0285] These results are attributed to the improved catalytic activity by pretreating the hydrogen-bonded lanthanide rare earth element compound and / or the oligomeric form of the lanthanide rare earth element compound, which causes a decrease in catalytic activity, prior to the alkylation reaction when preparing a catalyst composition for preparing a conjugated diene polymer.

[0286]

[0287] From these results, it was confirmed that the catalyst composition manufactured according to the method for manufacturing the catalyst composition of the present invention has excellent catalytic activity because it is manufactured by pretreating the hydrogen-bonded lanthanide rare earth element compound and / or the oligomer form of the lanthanide rare earth element compound, which causes a decrease in catalytic activity, prior to the alkylation reaction.

[0288] In addition, it was confirmed that the conjugated diene polymer manufactured according to the method for manufacturing a conjugated diene polymer of the present invention has a low content of lanthanide rare earth elements remaining in the conjugated diene polymer due to high catalytic activity, a high cis bond content and linearity, a narrow molecular weight distribution, and, when applied to a rubber composition, excellent wear resistance and low fuel consumption.

Claims

1. A pretreatment step (S10) for performing a pretreatment reaction of a hydrogen bond, oligomer form, or a combination thereof for a lanthanide series rare earth element compound; An alkylation reaction step (S20) of mixing and reacting a lanthanide rare earth element compound pretreated in a hydrogen bond, oligomer form, or a combination thereof in the above step (S10) with an alkylating agent; and In the above step (S20), it includes a halogenation reaction step (S30) of mixing and reacting the alkylated lanthanide rare earth element compound and the halide, The above step (S10) is performed by mixing and reacting a lanthanide series rare earth element compound and at least one trialkyl aluminum selected from the group consisting of tri-n-hexyl aluminum and tri-n-octyl aluminum, A method for producing a catalyst composition, wherein the above steps (S10), (S20), and (S30) are each performed in individual reactors connected in series.

2. In paragraph 1, A method for producing a catalyst composition, wherein the above step (S10) is performed before an alkylation reaction by trialkyl aluminum occurs for a lanthanide series rare earth element compound.

3. In paragraph 1, A method for manufacturing a catalyst composition wherein the above lanthanide series rare earth element compound is a neodymium compound represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R 1 Inland R 3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 Inland R 3 Not all of these are hydrogen.

4. In paragraph 1, The above lanthanide rare earth element compounds are Nd(2-ethyl hexanoate)3, Nd(2,2-dimethyl decanoate)3, Nd(2,2-diethyl decanoate)3, Nd(2,2-dipropyl decanoate)3, Nd(2,2-dibutyl decanoate)3, Nd(2,2-dihexyl decanoate)3, Nd(2,2-dioctyl decanoate)3, Nd(2-ethyl-2-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd(2-hexyl-2-octyl decanoate)3, Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl nonanoate)3, Nd(2,2-dihexyl A method for producing a catalyst composition, wherein the catalyst composition comprises at least one selected from the group consisting of Nd(2-ethyl-2-propyl nonanoate)3, Nd(2-ethyl-2-hexyl nonanoate)3, and Nd(2-ethyl-2-hexyl nonanoate).

5. In paragraph 1, A method for producing a catalyst composition, wherein the alkylating agent is an alkyl aluminum compound represented by the following chemical formula 2: [Chemical Formula 2] AlR 4 R 5 R 6 In the above chemical formula 2, R 4 Inland R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 4 Inland R 6 Not all of these are hydrogen, and do not include tri-n-hexyl aluminum and tri-n-octyl aluminum.

6. In paragraph 1, A method for producing a catalyst composition, wherein the above alkylating agent is dialkyl aluminum hydride.

7. In paragraph 1, A method for producing a catalyst composition, wherein the pretreatment reaction of the above step (S10), the alkylation reaction of the above step (S20), or the pretreatment reaction of the above step (S10) and the alkylation reaction of the above step (S20) are carried out by including a conjugated diene monomer.

8. In paragraph 1, A method for producing a catalyst composition, wherein the above halide is at least one selected from the group consisting of an alkyl aluminum halide represented by the following chemical formula 3 and an alkyl aluminum sesquihalide represented by the following chemical formula 4: [Chemical Formula 3] AlR 7 R 8 R 9 In the above chemical formula 3, R 7 Inland R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R 7 Inland R 9 Not all of them are halogens, [Chemical Formula 4] In the above chemical formula 4, R 10 Inland R 12 are each independently an alkyl group having 1 to 12 carbon atoms, X1 to X3 are each independently a halogen group.

9. In paragraph 1, A method for producing a catalyst composition, wherein the above halide is at least one selected from the group consisting of dialkyl aluminum halides and alkyl aluminum sesquihalides.

10. In paragraph 1, A method for producing a catalyst composition, wherein the above step (S20) is performed continuously in a plurality of reactors connected in series.

11. In paragraph 10, A method for producing a catalyst composition, wherein the above alkylating agent is divided and injected into a plurality of reactors connected in series.

12. In paragraph 1, A method for producing a catalyst composition, wherein the above steps (S10), (S20), and (S30) are performed sequentially.

13. A method for producing a conjugated diene polymer, comprising a step (S100) of producing an active polymer by polymerizing a conjugated diene monomer in the presence of a catalyst composition produced by the method for producing a catalyst composition according to claim 1, among hydrocarbon solvents.

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