Method for producing catalyst compositions and methods for producing conjugated diene polymers

Abstract

The present invention relates to a method for producing a catalyst composition with improved catalytic activity by pre-treating hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomeric forms of lanthanum-based rare earth element compounds, which cause a decrease in catalytic activity, and to a method for producing a conjugated diene polymer using the catalyst composition produced thereby.

Description

[Technical Field]

[0001] This invention claims priority under Korean Patent Application No. 10-2023-0082986 dated June 27, 2023, and all content disclosed in the said Korean Patent Application is incorporated herein by reference.

[0002] 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. [Background technology]

[0003] In recent years, with increasing concern for energy conservation and environmental issues, there has been a growing demand for more fuel-efficient automobiles. One method proposed to achieve this involves increasing the cis-bond content and linearity of polybutadiene in the rubber composition used for tire formation, while also narrowing the molecular weight distribution.

[0004] Polybutadiene can be produced using a Ziegler-Natta catalyst, which is produced by activating an organic acid metal compound with alkylaluminum and alkylaluminum halide compounds. The produced catalyst is then reacted with a 1,3-butadiene monomer to produce polybutadiene.

[0005] Here, examples of the aforementioned organic acid metal compounds include titanium-based, nickel-based, cobalt-based, and lanthanum-based compounds. From the viewpoint of increasing the cis-bond content and linearity of polybutadiene and narrowing the molecular weight distribution, lanthanum-based rare earth element compounds are mainly used.

[0006] Typical examples of lanthanum-based rare earth element compounds include neodymium compounds, with NdV (neodymium versatate) being a specific example. These compounds are activated by alkylation using alkylaluminum compounds followed by halogenation using alkylaluminum halide compounds. In order to stabilize the catalyst, 1,3-butadiene monomers are sometimes added during the alkylation reaction to perform prepolymerization.

[0007] In this case, lanthanum-based rare earth element compounds such as NdV do not exist in the form of single compounds, but rather in the form of hydrogen bonds formed by water and aliphatic compounds used in the manufacturing process, and / or in the form of oligomers (Non-Patent Literature 1 and Non-Patent Literature 2). However, when alkylation is immediately performed on hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomers of lanthanum-based rare earth element compounds, the alkylation takes longer and is not performed sufficiently compared to when the lanthanum-based rare earth element compound exists as a single compound. When such insufficiently alkylated lanthanum-based rare earth element compounds are introduced into a halogenation reactor for halogenation, it can reduce catalytic activity and increase contamination of the catalyst manufacturing equipment.

[0008] U.S. Patent Publication No. 9056303 (Patent Document 1) discloses a method for manufacturing a catalyst system using multiple alkylation reactors. Patent Document 1 describes a method for continuous manufacturing of catalyst systems to overcome the drawbacks of manufacturing them in batch mode. To prevent gel formation in the reactors and ensure the flexibility of the alkylating agent and rare earth element salts that affect catalytic activity, the type of reactor is specifically identified, the flow rate at the outlet of the catalyst system at the line outlet is adjusted as needed, and the system remains within a residual time range suitable for the alkylation and chlorination reactions. Furthermore, Japanese Patent Publication No. 5072191 (Patent Document 2) discloses a method for manufacturing a catalyst for conjugated diene polymerization by sequentially adding alkylaluminum compounds and alkylaluminum hydrides for the alkylation reaction. However, Patent Documents 1 and 2 only directly perform the alkylation reaction on lanthanum compounds during the manufacturing of the catalyst system and the catalyst for conjugated diene polymerization, and do not acknowledge the form of the lanthanum compounds added during the alkylation reaction or their effect on catalytic activity. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] US 9056303 B2 [Patent Document 2] JP 5072191 B2 [Non-patent literature]

[0010] [Non-Patent Document 1] "A Highly Reactive and Monomeric Neodymium Ctalyst", Macromolecules 2002, 35, 13, 4875-4879(https: / / doi.org / 10.1021 / ma012123p) [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) [Overview of the project] [Problems that the invention aims to solve]

[0011] The problem that the present invention aims to solve is to improve the catalytic activity of a catalyst composition for the polymerization of polybutadiene by pretreating it with hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomeric forms of lanthanum-based rare earth element compounds, which cause a decrease in catalytic activity, either before or simultaneously with the alkylation reaction.

[0012] In other words, the present invention aims to provide a method for producing a catalyst composition with improved catalytic activity by pre-treating hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomeric forms of lanthanum-based rare earth element compounds, which cause a decrease in catalytic activity, in order to solve the problems described in the background technology of the above invention.

[0013] Furthermore, the present invention aims to provide a method for producing a conjugated diene polymer with high cis bond content and linearity, and a narrow molecular weight distribution, by using a catalyst composition produced by the method for producing the catalyst composition described above. [Means for solving the problem]

[0014] To solve the above problems, the present invention provides a method for producing a catalyst composition and a method for producing a conjugated diene polymer. (1) The present invention comprises an alkylation reaction step (S10) in which a lanthanum-based rare earth element compound is mixed with an alkylating agent and reacted, and a halogenation reaction step (S20) in which the lanthanum-based rare earth element compound alkylated in step (S10) is mixed with a halide and reacted, wherein step (S10) is carried out including a pretreatment agent, or the lanthanum-based rare earth element compound in step (S10) is subjected to a pretreatment step (S1) in which hydrogen bonding, oligomer form, or a combination thereof is performed on the lanthanum-based rare earth element compound. The present invention provides a method for producing a catalyst composition, wherein the lanthanum-based rare earth element compound is pre-treated to have hydrogen bonds, oligomeric form, or a combination thereof, the pre-treatment agent is one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, and the (S1) step is carried out by mixing and reacting the lanthanum-based rare earth element compound with one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum.

[0015] (2) The present invention provides a method for producing the catalyst composition described in (1), wherein step (S1) is performed before the alkylation reaction with trialkylaluminum occurs with the lanthanum-based rare earth element compound.

[0016] (3) The present invention provides a method for producing the catalyst composition described in (1) or (2) above, wherein the lanthanum-based rare earth element compound is a neodymium compound represented by the following chemical formula 1.

[0017] [ka]

[0018] In the above chemical formula 1, R 1 ~R 3 Each is independently either hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 ~R 3Not all of it is hydrogen.

[0019] (4) In the present invention, the lanthanum-based rare earth element compound is Nd(2-ethylhexanoate)3, Nd(2,2-dimethyldecanoate)3, Nd(2,2-diethyldecanoate)3, Nd(2,2-dipropyldecanoate)3, Nd(2,2-dibutyldecanoate)3, Nd(2,2-dihexyldecanoate)3, Nd(2,2-dioctyldecanoate)3, Nd( 2-Ethyl-2-propyldecanoate)3, Nd(2-ethyl-2-butyldecanoate)3, Nd(2-ethyl-2-hexyldecanoate)3, Nd(2-propyl-2-butyldecanoate)3, Nd(2-propyl-2-hexyldecanoate)3, Nd(2-propyl-2-isopropyldecanoate)3, Nd(2-butyl-2-hexyldecanoate)3, Nd(2 Nd(2,2-Hexyl-2-Octyldecanoate)3, Nd(2,2-Diethyloctanoate)3, Nd(2,2-Dipropyloctanoate)3, Nd(2,2-Dibutyloctanoate)3, Nd(2,2-Dihexyloctanoate)3, Nd(2-Ethyl-2-Propyloctanoate)3, Nd(2-Ethyl-2-Hexyloctanoate)3, Nd(2,2-Diethylnonanoate) The present invention provides a method for producing the catalyst composition according to any one of the above (1) to (3), wherein the catalyst composition is one or more selected from the group consisting of Nd(2,2-dipropylnonanoate)3, Nd(2,2-dibutylnonanoate)3, Nd(2,2-dihexylnonanoate)3, Nd(2-ethyl-2-propylnonanoate)3, and Nd(2-ethyl-2-hexylnonanoate)3.

[0020] (5) The present invention provides a method for producing the catalyst composition according to any one of the above (1) to (4), wherein the alkylating agent is an alkylaluminum compound represented by the following chemical formula 2.

[0021] [Chemical formula 2] AlR 4 R 5 R 6

[0022] In Chemical Formula 2, R 4 ~R 6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, and not all of R 4 ~R 6 are hydrogen, and it does not include tri-n-hexylaluminum and tri-n-octylaluminum.

[0023] (6) In the present invention, there is provided a method for producing the catalyst composition according to any one of (1) to (5) above, wherein the alkylating agent is dialkylaluminum hydride.

[0024] (7) In the present invention, there is provided a method for producing the catalyst composition according to any one of (1) to (6) above, wherein the pretreatment reaction in the step (S1), the alkylation reaction in the step (S10), or the pretreatment reaction in the step (S1) and the alkylation reaction in the step (S10) are carried out in the presence of a conjugated diene monomer.

[0025] (8) In the present invention, there is provided a method for producing the catalyst composition according to any one of (1) to (7) above, wherein the halide is at least one selected from the group consisting of an alkylaluminum halide represented by the following Chemical Formula 3 and an alkylaluminum sesquihalide represented by the following Chemical Formula 4.

[0026] [Chemical Formula 3] AlR 7 R 8 R 9

[0027] In Chemical Formula 3, R 7 ~R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and not all of R 7 ~R 9 are halogen groups,

[0028] [Chemical Structure Diagram]

[0029] In the above chemical formula 4, R 10 ~R 12 Each of these is an alkyl group having 1 to 12 carbon atoms, and each of X1 to X3 is an alkyl group having 1 to 12 carbon atoms.

[0030] (9) The present invention provides a method for producing the catalyst composition according to any one of the above (1) to (8), wherein the halide is one or more selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides.

[0031] (10) The present invention provides a method for producing a conjugated diene polymer, comprising the step (S100) of polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition produced by any one of the methods for producing a catalyst composition described in (1) to (9) above, in order to produce an active polymer.

[0032] (11) The present invention provides a conjugated diene polymer produced by the method for producing a conjugated diene polymer described in (10) above. (12) The present invention provides a rubber composition comprising the conjugated diene polymer described in (11) above. [Effects of the Invention]

[0033] The catalyst composition produced by the method for producing the catalyst composition of the present invention exhibits excellent catalytic activity because it is produced by pre-treating hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomeric forms of lanthanum-based rare earth element compounds, which cause a decrease in catalytic activity, prior to the alkylation reaction.

[0034] The conjugated diene polymer produced by the present invention's method for producing conjugated diene polymers exhibits high catalytic activity, resulting in a low content of residual lanthanum rare earth elements, high cis bond content and linearity, a narrow molecular weight distribution, and excellent abrasion resistance and low fuel consumption when applied to rubber compositions. [Modes for carrying out the invention]

[0035] The present invention will now be described in more detail so that it can be easily understood. The terms and words used in the description and claims of this invention should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather should be interpreted in a manner consistent with the technical idea of ​​this invention, in accordance with the principle that inventors may appropriately define the concepts of terms in order to best describe their invention.

[0036] Method for producing catalyst compositions The present invention provides a method for producing a catalyst composition. The catalyst composition produced by the method for producing the catalyst composition may be a catalyst composition for the polymerization of conjugated diene polymers.

[0037] According to one embodiment of the present invention, a method for producing the catalyst composition includes an alkylation reaction step (S10) in which a lanthanum-based rare earth element compound is mixed with an alkylating agent and reacted, and a halogenation reaction step (S20) in which the lanthanum-based rare earth element compound alkylated in step (S10) is mixed with a halide and reacted, wherein step (S10) is carried out including a pretreatment agent, or the lanthanum-based rare earth element compound in step (S10) is pretreated by hydrogen bonding to the lanthanum-based rare earth element compound, oligomer form, or a combination thereof. The lanthanum-based rare earth element compound is pre-treated by a pre-treatment step (S1) to obtain hydrogen bonds, oligomeric form, or a combination thereof, wherein the pre-treatment agent is one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, and step (S1) may be carried out by mixing the lanthanum-based rare earth element compound with one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum and reacting them.

[0038] As described in the background technology of the present invention, lanthanum-based rare earth element compounds do not exist in the form of single compounds, but rather in the form of hydrogen bonds formed by water and aliphatic compounds used in the manufacturing process, and / or in the form of oligomers (see Non-Patent Documents 1 and 2). However, when an alkylation reaction is immediately performed on hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomers of lanthanum-based rare earth element compounds, the alkylation takes longer than when the lanthanum-based rare earth element compound exists as a single compound, and there is a problem that the alkylation reaction may not be carried out sufficiently. When such lanthanum-based rare earth element compounds that have not been sufficiently alkylated are introduced into a halogenation reactor for halogenation reactions, it can cause a decrease in catalytic activity and increase contamination of the catalyst manufacturing equipment. However, the method for producing the catalyst composition according to the present invention can improve catalytic activity by pre-treating the hydrogen-bonded lanthanum-based rare earth element compound and / or the oligomer form of the lanthanum-based rare earth element compound in step (S1) before the alkylation reaction, or by pre-treating the hydrogen-bonded lanthanum-based rare earth element compound and / or the oligomer form of the lanthanum-based rare earth element compound simultaneously with the alkylation reaction in step (S10). Here, the pre-treatment may include minimizing, or even removing, the hydrogen-bonded lanthanum-based rare earth element compound and / or the oligomer form of the lanthanum-based rare earth element compound before the alkylation reaction.

[0039] According to one embodiment of the present invention, when the lanthanum-based rare earth element compound is subjected to the pretreatment step (S1), the (S1) step may be carried out by mixing the lanthanum-based rare earth element compound with one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum and reacting them. It is known that tri-n-hexylaluminum and tri-n-octylaluminum can be used as alkylating agents in alkylation reactions. However, when tri-n-hexylaluminum and tri-n-octylaluminum are used simply as alkylating agents, rather than for the pretreatment reaction of step (S1) as in the present invention, it is necessary to induce an alkylation reaction with the lanthanum-based rare earth element compound depending on the purpose, which leads to the problem that the alkylation reaction takes a long time and the alkylation reaction is not carried out sufficiently. From this perspective, step (S1) may be performed before the alkylation reaction of the lanthanum-based rare earth element compound occurs with one or more trialkylaluminum compounds selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum. On the other hand, trialkylaluminum and / or dialkylaluminum hydrides that can be used as alkylating agents other than tri-n-hexylaluminum and tri-n-octylaluminum are not suitable as trialkylaluminum compounds for the pretreatment reaction in step (S1) because they cannot sufficiently induce hydrogen bonding, oligomeric form, or a combination thereof with respect to the lanthanum-based rare earth element compound.

[0040] According to one embodiment of the present invention, step (S1) may be carried out by adding one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum to 1 mole of lanthanum-based rare earth element compound in a molar ratio of 1 mole or more, 2 moles or more, 3 moles or more, 4 moles or more, 5 moles or more, 6 moles or more, 7 moles or more, 8 moles or more, 9 moles or more, or 10 moles or more, or by adding in a molar ratio of 20 moles or less, 19 moles or less, 18 moles or less, 17 moles or less, 16 moles or less, 15 moles or less, 14 moles or less, 13 moles or less, 12 moles or less, 11 moles or less, or 10 moles or less.

[0041] According to one embodiment of the present invention, step (S1) may be carried out at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, or 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.

[0042] According to one embodiment of the present invention, step (S1) 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, or for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0043] According to one embodiment of the present invention, step (S1) can further improve the efficiency of the pretreatment reaction for hydrogen bonding, oligomerization, or combination thereof with respect to the lanthanum-based rare earth element compound by adjusting the molar ratio of the lanthanum-based rare earth element compound to one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, the reaction temperature, and the reaction time.

[0044] According to one embodiment of the present invention, the lanthanum-based rare earth element compound may be a neodymium compound, specifically, neodymium carboxylate salts (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.); organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate) Salts, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl phosphate, etc.); organic phosphonates (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 decyl phosphonate, neodymium Dodecylphosphonate or neodymium octadecylphosphonate, etc.); organophosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl)phosphinate, or neodymium (2-ethylhexyl)phosphinate, etc.); carbamate (e.g., neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, Neodymium dibutylcarbamate or neodymium dibenzylcarbamate, etc.); dithiocarbamate (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, or neodymium dibutyldithiocarbamate, etc.); xanthogenic acid (e.g., neodymium methylxanthogenic acid, neodymium ethylxanthogenic acid, neodymium isopropylxanthogenic acid, neodymium butylxanthogenic acid, or neodymium benzylxanthogenic acid, etc.);β-diketonates (e.g., neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, or neodymium benzoylacetonate); alkoxides or allyl oxides (e.g., neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide, or neodymium nonylphenoxide); halides or pseudohalides (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, and Examples include neodymium azides, oxyhalides (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide), or organoneodymium 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, where Ln is a rare earth metal element and R is a hydrocarbyl group), and may contain one or more of these or mixtures of two or more.

[0045] According to one embodiment of the present invention, the lanthanum-based rare earth element compound may be a neodymium compound represented by the following chemical formula 1.

[0046] [ka]

[0047] In the above chemical formula 1, R 1 ~R 3 Each is independently either hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 1 ~R 3 It is not necessary for all of them to be hydrogen. Specifically, in the above chemical formula 1, R 1 R is an alkyl group having 4 to 12 carbon atoms. 2 and R 3 Each is independently either hydrogen or an alkyl group having 2 to 8 carbon atoms, and R 2 and R3 It is not necessary for all of them to be hydrogen. More specifically, in the above chemical formula 1, R 1 R is an alkyl group having 6 to 8 carbon atoms. 2 and R 3 Each is independently either hydrogen or an alkyl group having 2 to 6 carbon atoms, and R 2 and R 3 It doesn't have to be all hydrogen.

[0048] According to one embodiment of the present invention, the lanthanum-based rare earth element compound is Nd(2-ethylhexanoate)3 (neodymium versate), Nd(2,2-dimethyldecanoate)3, Nd(2,2-diethyldecanoate)3, Nd(2,2-dipropyldecanoate)3, Nd(2,2-dibutyldecanoate)3, Nd(2,2-dihexyldecanoate)3, Nd(2, 2-Dioctyldecanoate)3, Nd(2-ethyl-2-propyldecanoate)3, Nd(2-ethyl-2-butyldecanoate)3, Nd(2-ethyl-2-hexyldecanoate)3, Nd(2-propyl-2-butyldecanoate)3, Nd(2-propyl-2-hexyldecanoate)3, Nd(2-propyl-2-isopropyldecanoate)3, Nd(2- Butyl-2-hexyldecanoate)3, Nd(2-hexyl-2-octyldecanoate)3, Nd(2,2-diethyloctanoate)3, Nd(2,2-dipropyloctanoate)3, Nd(2,2-dibutyloctanoate)3, Nd(2,2-dihexyloctanoate)3, Nd(2-ethyl-2-propyloctanoate)3, Nd(2-ethyl-2-hexyl It may be one or more selected from the group consisting of syloctanoate)3, Nd(2,2-diethylnonanoate)3, Nd(2,2-dipropylnonanoate)3, Nd(2,2-dibutylnonanoate)3, Nd(2,2-dihexylnonanoate)3, Nd(2-ethyl-2-propylnonanoate)3, and Nd(2-ethyl-2-hexylnonanoate)3.

[0049] According to one embodiment of the present invention, the neodymium compound contains a carboxylate ligand with alkyl groups of various lengths having 2 or more carbon atoms as substituents at the α-position. This induces steric changes around the neodymium central metal, thereby blocking entanglement between compounds. This has the effect of suppressing oligomerization during polymerization of conjugated diene polymers using the catalyst composition. Furthermore, such neodymium compounds have high solubility in solvents, and the proportion of neodymium located in the central region, which is difficult to convert to catalytically active species, is reduced, resulting in a high conversion rate to catalytically active species.

[0050] 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 nonpolar solvent at room temperature (25°C). The solubility of the neodymium compound refers to the degree to which it dissolves transparently without turbidity, and by exhibiting such high solubility, it is possible to demonstrate excellent catalytic activity.

[0051] According to one embodiment of the present invention, step (S1) may include a conjugated diene monomer. This is for forming a preforming or premix catalyst composition by pre-mixing a conjugated diene monomer, which is used in the polymerization reaction of a conjugated diene polymer using the catalyst composition produced by the present invention, with the catalyst composition. This can further improve the activity of the catalyst composition and stabilize the active polymer produced. "Preforming" may mean that a small amount of a conjugated diene monomer, such as 1,3-butadiene, is added to the catalyst composition containing a neodymium compound, an alkylating agent, and a halide, i.e., to reduce the possibility of generating active species of various catalyst compositions in the catalyst system, and that pre-polymerization is performed in the catalyst composition system along with the addition of 1,3-butadiene. "Premix" may mean that polymerization is not performed in the catalyst composition system, and each compound is uniformly mixed.

[0052] According to one embodiment of the present invention, the conjugated diene monomer that can be introduced in step (S1) 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, or it may be 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, or 2,4-hexadiene.

[0053] According to one embodiment of the present invention, when step (S1) is carried out including a conjugated diene monomer, the conjugated diene monomer may be added in a molar ratio of 1 mole or more, 5 moles or more, 10 moles or more, 15 moles or more, or 20 moles or more per mole of lanthanum-based rare earth element compound, or in a molar ratio of 100 moles or less, 90 moles or less, 80 moles or less, 70 moles or less, 60 moles or less, or 50 moles or less.

[0054] According to one embodiment of the present invention, step (S10) is a step for carrying out an alkylation reaction of a lanthanum-based rare earth element compound, and may be carried out by mixing and reacting a lanthanum-based rare earth element compound that has been pretreated in step (S1) for hydrogen bonding, oligomer form, or a combination thereof with an alkylating agent, or by mixing and reacting an unpretreated lanthanum-based rare earth element compound with a pretreatment agent and an alkylating agent. Here, the unpretreated lanthanum-based rare earth element compound is the same as the lanthanum-based rare earth element compound described above.

[0055] According to one embodiment of the present invention, if step (S10) is carried out including a pretreatment agent, step (S10) may be carried out by mixing and reacting a lanthanum-based rare earth element compound with the pretreatment agent and an alkylating agent, and the pretreatment agent may carry out a pretreatment reaction to the lanthanum-based rare earth element compound by forming hydrogen bonds, an oligomeric form, or a combination thereof. Tri-n-hexylaluminum and tri-n-octylaluminum are known to be usable as alkylating agents in alkylation reactions. However, if tri-n-hexylaluminum and tri-n-octylaluminum are used alone as alkylating agents, rather than for carrying out a pretreatment reaction in step (S10) as in the present invention, it is necessary to induce an alkylation reaction with the lanthanum-based rare earth element compound depending on the purpose, which causes the alkylation reaction to take a long time and results in the problem that the alkylation reaction does not carry out sufficiently. On the other hand, trialkylaluminum and / or dialkylaluminum hydrides that can be used as alkylating agents other than the aforementioned tri-n-hexylaluminum and tri-n-octylaluminum are not suitable as pretreatment agents for the pretreatment reaction during the alkylation reaction in step (S10) because they cannot sufficiently induce hydrogen bonding, oligomerization, or combinations thereof with lanthanum-based rare earth element compounds.

[0056] According to one embodiment of the present invention, step (S10) may be carried out by adding one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum to 1 mole of lanthanum-based rare earth element compound in a molar ratio of 1 mole or more, 2 moles or more, 3 moles or more, 4 moles or more, 5 moles or more, 6 moles or more, 7 moles or more, 8 moles or more, 9 moles or more, 10 moles or more, 11 moles or more, 12 moles or more, 13 moles or more, 14 moles or more, 15 moles or more, 16 moles or more, 17 moles or more, 18 moles or more, 19 moles or more, or 20 moles or less. Alternatively, it may be carried out by adding 30 moles or less, 29 moles or less, 28 moles or less, 27 moles or less, 26 moles or less, 25 moles or less, 24 moles or less, 23 moles or less, 22 moles or less, 21 moles or less, or 20 moles or less.

[0057] According to one embodiment of the present invention, step (S10) may be carried out at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, or 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.

[0058] According to one embodiment of the present invention, 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, or for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0059] According to one embodiment of the present invention, step (S10) can further improve the efficiency of the pretreatment reaction for hydrogen bonding, oligomerization, or combination thereof with respect to the lanthanum-based rare earth element compound by adjusting the molar ratio of the lanthanum-based rare earth element compound to one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum, the reaction temperature, and the reaction time.

[0060] According to one embodiment of the present invention, the alkylating agent can act as a co-catalyst as an organometallic compound capable of transferring a hydrocarbyl group to another metal. The alkylating agent may be an organometallic compound that is soluble in the polymerization solvent and contains a metal-carbon bond, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound.

[0061] According to one embodiment of the present invention, the alkylating agent may be an organoaluminum compound, specifically, alkylaluminum such as tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, and phenylisobutylaluminum hydride. Dihydrocarbyl aluminum hydrides such as 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 hydride, benzylisopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzylisobutyl aluminum hydride, or benzyl-n-octyl aluminum hydride; or hydrocarbyl aluminum 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.

[0062] According to one embodiment of the present invention, the alkylating agent is preferably an alkylaluminum compound, from the viewpoint of controlling the catalytic reaction and side reactions by a lanthanum-based rare earth element compound pretreated in step (S1) in terms of hydrogen bonding, oligomer form, or a combination thereof, or by a lanthanum-based rare earth element compound pretreated in step (S10) in terms of hydrogen bonding, oligomer form, or a combination thereof by a pretreatment agent. Specifically, the alkylating agent may be an alkylaluminum compound represented by the following chemical formula 2.

[0063] [Chemical formula 2] AlR 4 R 5 R 6

[0064] In the above chemical formula 2, R 4 ~R 6 Each is independently either hydrogen or an alkyl group having 1 to 12 carbon atoms, and R 4 ~R 6 It is not the case that all of it is hydrogen, and it does not have to contain tri-n-hexylaluminum and tri-n-octylaluminum. Specifically, in the above chemical formula 2, R 4 ~R 6 Each is independently either hydrogen or an alkyl group having 3 to 8 carbon atoms, and R 4 ~R 6 It is not the case that all of them are hydrogen, and it does not have to contain tri-n-hexylaluminum and tri-n-octylaluminum. More specifically, in the above chemical formula 2, R 4 ~R 6 Each is independently either hydrogen or an alkyl group having 3 to 5 carbon atoms, and R 4 ~R 6 It doesn't have to be all hydrogen.

[0065] According to one embodiment of the present invention, the alkylating agent may be a dialkylaluminum hydride, from the viewpoint of controlling the catalytic reaction and side reactions by a lanthanum-based rare earth element compound pretreated in step (S1) in terms of hydrogen bonding, oligomer form, or a combination thereof, or by a lanthanum-based rare earth element compound pretreated in step (S10) in terms of hydrogen bonding, oligomer form, or a combination thereof by a pretreatment agent, and the type of dialkylaluminum hydride is as described above. Specifically, the alkylating agent may be diisobutylaluminum hydride.

[0066] According to one embodiment of the present invention, the alkylating agent may comprise two or more alkylaluminum compounds. Specifically, the alkylating agent may comprise two or more compounds selected from the group consisting of dialkylaluminum hydride and trialkylaluminum. More specifically, the alkylating agent may comprise one or more dialkylaluminum hydride and one or more trialkylaluminum, and even more specifically, the alkylating agent may comprise diisobutylaluminum hydride and triisobutylaluminum.

[0067] According to one embodiment of the present invention, step (S10) may be carried out by adding an alkylating agent in a molar ratio of 1 mole or more, 2 moles or more, 3 moles or more, 4 moles or more, 5 moles or more, 6 moles or more, 7 moles or more, 8 moles or more, 9 moles or more, 10 moles or more, 11 moles or more, 12 moles or more, 13 moles or more, 14 moles or more, or 15 moles or more per mole of a lanthanum-based rare earth element compound, or a lanthanum-based rare earth element compound pretreated in the form of hydrogen bonds, oligomers, or a combination thereof as described in step (S1), or by adding an alkylating agent in a molar ratio of 1 mole or more, 2 moles or more, 3 moles or more, 4 moles or more, 5 moles or more, 6 moles or more, 7 moles or more, 8 moles or more, 9 moles or more, 10 moles or more, 11 moles or more, 12 moles or more, 13 moles or more, 14 moles or more, or 15 moles or less.

[0068] According to one embodiment of the present invention, step (S10) may be carried out at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, or 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.

[0069] According to one embodiment of the present invention, 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 2 hours or less, 1 hour 30 minutes or less, 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0070] According to one embodiment of the present invention, step (S10) can be further improved by adjusting the molar ratio of the lanthanum-based rare earth element compound, or the hydrogen bond, oligomer form, or combination thereof pretreated lanthanum-based rare earth element compound in step (S1), the alkylating agent, the reaction temperature, and the reaction time.

[0071] According to one embodiment of the present invention, step (S10) may be carried out including a conjugated diene monomer for the same purposes as step (S1). In this case, when step (S10) is carried out including a conjugated diene monomer, it may be carried out separately from or simultaneously with step (S1).

[0072] According to one embodiment of the present invention, when step (S10) is carried out including a conjugated diene monomer, the conjugated diene monomer may be added in a molar ratio of 1 mole or more, 5 moles or more, 10 moles or more, 15 moles or more, or 20 moles or more per mole of a lanthanum-based rare earth element compound that has been pretreated in the form of hydrogen bonds, oligomers, or a combination thereof in step (S1), or it may be added in a molar ratio of 100 moles or less, 90 moles or less, 80 moles or less, 70 moles or less, 60 moles or less, or 50 moles or less.

[0073] According to one embodiment of the present invention, step (S20) is a step for carrying out a halogenation reaction with the lanthanum-based rare earth element compound alkylated in step (S10), and may be carried out by mixing the lanthanum-based rare earth element compound alkylated in step (S10) with a halide and reacting them.

[0074] According to one embodiment of the present invention, the halide may be an elemental halogen, an interhalogen compound, a hydrogen halide, an organic halide, a nonmetallic halide, a metal halide, or an organometallic halide.

[0075] According to one embodiment of the present invention, the halogen element may be fluorine, chlorine, bromine, or iodine. According to one embodiment of the present invention, the interhalogen compound may be an iodo monochloride, iodo monobromide, iodo trichloride, iodo pentafluoride, iodo monofluoride, or iodo trifluoride.

[0076] According to one embodiment of the present invention, the hydrogen halogen may be hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide. 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-diphenylmethane, bromo-diphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methylchloroformate, methylbromoformate, iodomethane, diiodomethane, triiodomethane (also called "iodoform"). It may also be 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 methyliodoformate, etc.

[0077] According to one embodiment of the present invention, the nonmetallic 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, etc.

[0078] 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 dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

[0079] According to one embodiment of the present invention, the organometallic halide may be an alkylaluminum halide or an alkylaluminum sesquihalide. Specifically, the organometallic halide may be dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-t-butyltin di Chloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide, methylmagnesium iodide, dimethylaluminum iodide, diethylaluminum iodide, di-n-butylaluminum iodide, diisobutylaluminum iodide, di-n-octylaluminum iodide, methylaluminum iodide, ethylaluminum iodide, n-butylaluminum iodide, i These may include sobutylaluminum diiodide, methylaluminum sesquiiodide, ethylaluminum sesquiiodide, isobutylaluminum sesquiiodide, ethylmagnesium iodide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin diiodide, or di-t-butyltin diiodide.

[0080] According to one embodiment of the present invention, the halogen may be one or more selected from the group consisting of alkylaluminum halides represented by the following chemical formula 3 and alkylaluminum sesquihalides represented by the following chemical formula 4, from the viewpoint of improving catalytic activity and thereby improving reactivity.

[0081] [Chemical formula 3] AlR 7 R 8 R 9

[0082] In the above chemical formula 3, R 7 ~R 9 Each of these is independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R 7 ~R 9 Not all of them are halogen groups. Specifically, in the above chemical formula 3, R 7 ~R 9 Each of these is independently a halogen group or an alkyl group having 1 to 6 carbon atoms, and R 7 ~R 9 Not all of them are halogen groups. More specifically, in the above chemical formula 3, R 7 and R 8 Each of these is an alkyl group having 1 to 4 carbon atoms, and R 9 This may be a halogen group.

[0083] [ka]

[0084] In the above chemical formula 4, R 10 ~R 12 Each of these may independently be an alkyl group having 1 to 12 carbon atoms, and each of X1 to X3 may independently be a halogen group. Specifically, in the above chemical formula 4, R 10 ~R 12 Each of these may independently be an alkyl group having 1 to 6 carbon atoms. More specifically, in the above chemical formula 4, R 10 ~R 12Each of these may independently be an alkyl group having 1 to 4 carbon atoms.

[0085] According to one embodiment of the present invention, the halide may be one or more selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides, from the viewpoint of controlling the catalytic reaction and side reactions by a lanthanum-based rare earth element compound pretreated in step (S1) for hydrogen bonding, oligomer form, or a combination thereof, or by a lanthanum-based rare earth element compound pretreated in step (S10) for hydrogen bonding, oligomer form, or a combination thereof by a pretreatment agent, and the types of dialkylaluminum halides and alkylaluminum sesquihalides are as described above. Specifically, the dialkylaluminum halide may be diethylaluminum chloride, and the alkylaluminum sesquihalide may be ethylaluminum sesquichloride.

[0086] According to one embodiment of the present invention, step (S20) may be carried out by adding a halide in a molar ratio of 0.1 moles or more, 0.5 moles or more, 1.0 moles or more, 1.5 moles or more, 2.0 moles or more, 2.5 moles or more, or 3.0 moles or more per mole of a lanthanum-based rare earth element compound, or a lanthanum-based rare earth element compound pretreated in the form of hydrogen bonds, oligomers, or a combination thereof as described in step (S1), or by adding a halide in a molar ratio of 5.0 moles or less, 4.5 moles or less, 4.0 moles or less, 3.5 moles or less, or 3.0 moles or less.

[0087] According to one embodiment of the present invention, step (S20) may be performed at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, or 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.

[0088] According to one embodiment of the present invention, 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, or for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0089] According to one embodiment of the present invention, step (S20) can further improve catalytic activity by adjusting the molar ratio of the lanthanum-based rare earth element compound pretreated in step (S1) for hydrogen bonding, oligomer form, or a combination thereof, to the halide, the reaction temperature, and the reaction time within step (S10).

[0090] According to one embodiment of the present invention, steps (S1), (S10), and (S20) may be carried out in an organic solvent. The organic solvent may be a nonpolar solvent that does not react with the components of the catalyst composition. Specifically, 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 an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, or xylene. More specifically, the organic solvent may be a linear, branched, or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, preferably n-hexane, cyclohexane, or a mixture thereof.

[0091] According to one embodiment of the present invention, steps (S1), (S10), and (S20) may be carried out in a batch reactor. Alternatively, steps (S1), (S10), and (S20) may be carried out by sequentially adding the lanthanum-based rare earth element compound, trialkylaluminum, alkylating agent, and halide in each step.

[0092] According to one embodiment of the present invention, steps (S1), (S10), and (S20) may be carried out in separate reactors connected in series. Therefore, in order to continuously produce catalysts by the method for producing the catalyst composition, two or more reactors are required.

[0093] According to one embodiment of the present invention, steps (S1), (S10), and (S20) may be carried out in sequence. That is, steps (S1), (S10), and (S20) may be carried out in sequence in separate reactors connected in series. In this case, the productivity of the catalyst composition and the conjugated diene polymer using the same can be improved, and more uniform quality can be ensured.

[0094] According to one embodiment of the present invention, step (S10) may be carried out continuously in a plurality of reactors connected in series. In this case, by carrying out the alkylation reaction in a plurality of reactors connected in series, the alkylation reaction can be carried out sufficiently, and the activity of the catalyst composition can be further improved. In this case, the pretreatment agent and / or alkylating agent may be added only to the first of the plurality of reactors connected in series to carry out step (S10), or it may be divided and added to the plurality of reactors connected in series to carry out step (S10). When the pretreatment agent and / or alkylating agent is divided and added to a plurality of reactors, the reactors to which the pretreatment agent and / or alkylating agent is added can be selected as needed. Furthermore, the types of pretreatment agent and / or alkylating agent added to each reactor may be the same or different when divided and added to the plurality of reactors connected in series.

[0095] According to one embodiment of the present invention, at least one of the multiple reactors connected in series in step (S10) may include a pipe-type reactor equipped with a line mixer. In this case, continuous mixing of the reactants is possible by allowing them to remain in the pipe-type reactor connected between the reactors connected in series, thereby allowing the alkylation reaction to proceed more sufficiently.

[0096] According to one embodiment of the present invention, all steps of the method for producing the catalyst composition, including steps (S1), (S10), and (S20), may be carried out at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, or 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.

[0097] According to one embodiment of the present invention, all steps of the method for producing the catalyst composition, including steps (S1), (S10), and (S20), may be carried out for 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, or 70 minutes or more, or for 2 hours or less, 1 hour 50 minutes or less, 1 hour 40 minutes or less, 1 hour 30 minutes or less, 1 hour 20 minutes or less, or 1 hour 10 minutes or less.

[0098] Method for producing conjugated diene polymers This invention provides a method for producing conjugated diene polymers. According to one embodiment of the present invention, the method for producing the conjugated diene polymer may include the step (S100) of polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition produced by the method for producing the catalyst composition to produce an active polymer.

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

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

[0101] According to one embodiment of the present invention, the catalyst composition may be a catalyst composition produced by the method for producing the catalyst composition 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 per 100 g of conjugated diene monomer, or 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 more.

[0102] According to one embodiment of the present invention, the polymerization in step (S100) may be carried out by continuous polymerization in a polymerization reactor including at least two reactors, or by batch polymerization in a batch reactor. The polymerization may also be temperature-controlled polymerization, isothermal polymerization, or constant-temperature polymerization (adiabatic polymerization).

[0103] According to one embodiment of the present invention, constant-temperature polymerization means polymerization using the reaction heat of the catalyst composition itself without adding any heat after it has been added, temperature-increasing polymerization means increasing the temperature by adding heat after it has been added, and isothermal polymerization means maintaining a constant temperature of the reactants by adding heat to increase the heat or removing heat after it has been added.

[0104] According to one embodiment of the present invention, the polymerization in 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 more specifically, solution polymerization.

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

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

[0107] According to one embodiment of the present invention, the conjugated diene polymer formed by polymerization in step (S100) may be an active polymer containing a site activated by the catalyst composition.

[0108] According to one embodiment of the present invention, the process may include a step (S200) of reacting the active polymer with a modifying agent. The modifying agent may be a known modifying agent that can be used in the production of conjugated diene polymers using a catalyst composition containing a lanthanum-based rare earth element compound.

[0109] According to one embodiment of the present invention, the method for producing the conjugated diene polymer may include a step of further terminating the polymerization by using an additive such as a reaction termination agent to complete the polymerization reaction, such as polyoxyethylene glycol phosphate, or an antioxidant such as 2,6-di-t-butyl paracresol, after the production of the active polymer. In addition, additives that facilitate solution polymerization, such as chelating agents, dispersants, pH adjusters, oxygen scavengers, or oxygen scavengers, may be selectively used along with the reaction termination agent.

[0110] Conjugated diene polymers This invention provides conjugated diene polymers. According to one embodiment of the present invention, the conjugated diene polymer may be produced by the method for producing the conjugated diene polymer. That is, the conjugated diene polymer may be polymerized in the presence of a catalyst composition produced by the method for producing the catalyst composition described above.

[0111] According to one embodiment of the present invention, the conjugated diene polymer may contain conjugated diene monomer units. The conjugated diene monomer units refer to repeating units formed by the polymerization of conjugated diene monomers.

[0112] According to one embodiment of the present invention, the conjugated diene polymer may contain 80% or more, 85% or more, 90% or more, 95% or more, or 100% by weight of 1,3-butadiene monomer units, and may also contain 20% or less, 15% or less, 10% or less, or 5% or less by weight of other conjugated diene monomer units that can be selectively copolymerized with the 1,3-butadiene monomer. Within this range, a decrease in the cis-1,4 bond content in the conjugated diene polymer can be prevented. The 1,3-butadiene monomer may be 1,3-butadiene or a derivative thereof, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. Other conjugated diene monomers copolymerizable with 1,3-butadiene may be 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, or 2,4-hexadiene.

[0113] According to one embodiment of the present invention, the conjugated diene polymer may be a conjugated diene polymer catalyzed from a catalyst composition containing a lanthanum-based rare earth element compound. That is, the conjugated diene polymer may be a conjugated diene polymer containing an organometallic moiety activated from a catalyst composition containing a neodymium compound.

[0114] According to one embodiment of the present invention, the conjugated diene polymer has a weight-average molecular weight (Mw) of 1.0 × 10⁻⁶5 above g / mol, 2.0×10 5 above g / mol, 3.0×10 5 above g / mol, 4.0×10 5 above g / mol, 5.0×10 5 above g / mol, 6.0×10 5 above g / mol, 7.0×10 5 above g / mol, 8.0×10 5 above g / mol, or 9.0×10 5 may also be above g / mol, and 1.0×10 6 below g / mol, 9.0×10 5 below g / mol, 8.0×10 5 below g / mol, 7.0×10 5 below g / mol, 6.0×10 5 below g / mol, 5.0×10 5 below g / mol, 4.0×10 5 below g / mol, or 3.0×10 5 may also be below g / mol. Further, the conjugated diene polymer has a number average molecular weight (Mn) of 1.0×10 5 above g / mol, 2.0×10 5 above g / mol, 3.0×10 5 above g / mol, 4.0×10 5 above g / mol, or 5.0×10 5 may also be above g / mol, and 6.0×10 5 below g / mol, 5.0×10 5 below g / mol, 4.0×10 5 below g / mol, 3.0×10 5 below g / mol, 2.0×10 5 below g / mol, or 1.0×10 5 may also be below g / mol. When applied to a rubber composition within this range, there are effects such as excellent tensile properties, excellent processability, easy kneading due to improved workability of the rubber composition, and excellent mechanical properties and property balance of the rubber composition.

[0115] 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 number average molecular weight (Mn) to the weight average molecular weight (Mw). In this case, the number average molecular weight (Mn) is the common average of the individual polymer molecular weights calculated by measuring the molecular weights of n polymer chains, summing these molecular weights, and dividing by n, while 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). Furthermore, the weight average molecular weight and the number average molecular weight may each refer to the polystyrene-equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0116] According to one embodiment of the present invention, when the conjugated diene polymer 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, it has the effect of exhibiting excellent tensile properties, viscoelasticity, and processability for the rubber composition, as well as an excellent balance of these physical properties.

[0117] According to one embodiment of the present invention, the conjugated diene polymer may have a cis-1,4 bond content of 96.0% or more by weight, 96.1% or more by weight, 96.2% or more by weight, 96.3% or more by weight, 96.4% or more by weight, 96.5% or more by weight, 96.6% or more by weight, 96.7% or more by weight, 96.8% or more by weight, 96.9% or more by weight, 97.0% or more by weight, 97.1% or more by weight, 97.2% or more by weight, 97.3% or more by weight, 97.4% or more by weight, 97.5% or more by weight, 97.6% or more by weight, 97.9% or more by weight, 98.0% or more by weight, 98.1% or more by weight, or 98.2% or more by weight, and may also have a cis-1,4 bond content of 96.0% or more by weight, 96.1% or more by weight, or 98.2% or more by weight, or 100.0% or less by weight, 99.5% or less by weight, or 99.0% or less by weight.

[0118] According to one embodiment of the present invention, the conjugated diene polymer may have a Mooney viscosity (ML1+4, @100℃) of 30 or more, 31 or more, 32 or more, 33 or more, 34 or more, 35 or more, 36 or more, 37 or more, 38 or more, 39 or more, 40 or more, 41 or more, 42 or more, or 43 or more, and may also have a Mooney viscosity of 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, 49 or less, 48 ​​or less, or 47 or less.

[0119] rubber composition This invention provides a rubber composition. According to one embodiment of the present invention, the rubber composition may contain the conjugated diene polymer. Specifically, the rubber composition may contain 0.1% or more by weight, 10% or more by weight, or 20% or more by weight of the conjugated diene polymer, or it may contain 100% or less by weight, 95% or less by weight, or 90% or less by weight. Within this range, the wear resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, can be sufficiently ensured.

[0120] According to one embodiment of the present invention, the rubber composition may further contain other rubber components as needed, in addition to the conjugated diene polymer. In this case, the rubber components may be included in an amount of 90% by weight or less of the total weight of the rubber composition. Specifically, they may be included in an amount of 1 to 900 parts by weight per 100 parts by weight of the conjugated diene copolymer.

[0121] According to one embodiment of the present invention, the rubber component may be natural rubber or synthetic rubber, for example, the rubber component may be natural rubber containing cis-1,4-polyisoprene (NR); modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), or hydrogenated natural rubber, which are obtained by modifying or refining the general natural rubber; styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, or polyisobutylene-co-isoprene. The material may be synthetic rubber such as 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, or one or more of these mixtures.

[0122] According to one embodiment of the present invention, the rubber composition may contain 20 to 90 parts by weight of a filler per 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. Specifically, the filler may be a carbon black-based filler.

[0123] According to one embodiment of the present invention, the carbon black-based filler has a nitrogen adsorption specific surface area (N2SA, measured in accordance with JIS K6217-2:2001) of 20 m². 2 / g~250m 2 It may be / g. When within this range, the processability of the rubber composition is excellent, and sufficient reinforcement performance by the filler can be ensured. Furthermore, the carbon black-based filler may have a dibutyl phthalate oil absorption rate (DBP) of 80cc / 100g to 200cc / 100g. When within this range, the processability of the rubber composition is excellent, and sufficient reinforcement performance by the filler can be ensured.

[0124] According to one embodiment of the present invention, the silica-based filler may be wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica-based filler may be wet silica, which exhibits the most significant effect in both improving fracture properties and wet grip. Furthermore, the silica-based filler may have a nitrogen adsorption specific surface area (nitrogen surface area per gram, N2SA) of 120 m². 2 / g~180m 2 The specific surface area for adsorption of CTAB (cetyl trimethyl ammonium bromide) is 100 m² / g. 2 / g~200m 2 It may also be / g. When within this range, the rubber composition exhibits excellent processability, and sufficient reinforcement performance by the filler can be ensured.

[0125] According to one embodiment of the present invention, when a silica-based filler is used as the filler, a silane coupling agent may also be used to improve reinforcing properties and low heat generation. The 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- The silane coupling agent may be dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, etc. Specifically, considering the effect of improving reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

[0126] According to one embodiment of the present invention, the rubber composition may be sulfur crosslinkable, and thereafter may further contain a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder and may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component. Within this range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, as well as low fuel consumption.

[0127] According to one embodiment of the present invention, the rubber composition may further contain, in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, antioxidants, scorch inhibitors, zinc white, stearic acid, thermosetting resins, or thermoplastic resins.

[0128] According to one embodiment of the present invention, the vulcanization accelerator is not particularly limited, and may specifically be a thiazole compound such as M (2-mercaptobenzothiazole), DM (dibenzothiadyl disulfide), or CZ (N-cyclohexyl-2-benzothiadylsulfenamide), or a guanidine compound such as DPG (diphenylguanidine). The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the rubber component.

[0129] According to one embodiment of the present invention, the process oil acts as a softening agent in the rubber composition and may be a paraffinic, naphthenic, or aromatic compound. More specifically, an aromatic process oil may be used when considering tensile strength and abrasion resistance, while a naphthenic or paraffinic process oil may be used when considering hysteresis loss and low-temperature properties. The process oil may be included in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component. Within this range, a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber can be prevented.

[0130] According to one embodiment of the present invention, the antioxidant 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 antioxidant may be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of the rubber component.

[0131] According to one embodiment of the present invention, the rubber composition can be obtained by kneading using a kneader such as a Banbury mixer, roll mixer, or internal mixer, depending on the formulation, and after molding, a vulcanization process can be performed to obtain a rubber composition that is low in heat generation and has excellent abrasion resistance.

[0132] According to one embodiment of the present invention, the rubber composition is useful for manufacturing various tire components such as tire treads, under treads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, chafers, or bead coating rubber, as well as various industrial rubber products such as dustproof rubber, belt conveyors, and hoses. Specifically, a molded article manufactured using the rubber composition may include a tire or a tire tread.

[0133] The embodiments of the present invention will be described in detail below so that they can be easily implemented by a person with ordinary skill in the art to which the present invention pertains. However, the present invention may be realized in various different forms and is not limited to the embodiments described herein.

[0134] Examples and Comparative Examples Example 1 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.3 g of tri-n-octylaluminum and 0.8 g of diisobutylaluminum hydride were added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0135] Example 2 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.0 g of tri-n-hexylaluminum and 0.8 g of diisobutylaluminum hydride were added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0136] Example 3 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.3 g of tri-n-octylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.8 g of diisobutylaluminum hydride was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0137] Example 4 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.0 g of tri-n-octylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 2.1 g of triisobutylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0138] Example 5 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 2.6 g of tri-n-octylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.8 g of diisobutylaluminum hydride was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0139] Example 6 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.3 g of tri-n-octylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.8 g of diisobutylaluminum hydride was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of ethylaluminum sesquichloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0140] Example 7 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.0 g of tri-n-hexylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.8 g of diisobutylaluminum hydride was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0141] Example 8 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.0 g of tri-n-hexylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 2.1 g of triisobutylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0142] Example 9 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 2.0 g of tri-n-hexylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.8 g of diisobutylaluminum hydride was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0143] Example 10 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 1.0 g of tri-n-hexylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.8 g of diisobutylaluminum hydride was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of ethylaluminum sesquichloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0144] Comparative Example 1 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 0.8 g of diisobutylaluminum hydride was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Next, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0145] Comparative Example 2 2.1 g of 1,3-butadiene diluted to a concentration of 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versate (Solvay) diluted to a concentration of 40 wt% in n-hexane was added. Next, 2.1 g of triisobutylaluminum was added to the reactor at a temperature of 10°C and stirred for 30 minutes. Then, 0.1 g of diethylaluminum chloride was added to the reactor at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0146] Experimental example Experimental Example 1: Production of conjugated diene polymers and evaluation of the activity of catalyst compositions 500 g of 1,3-butadiene and 4.2 kg of n-hexane were placed in a 20 L autoclave reactor, and the internal temperature of the reactor was raised to 70°C. When using the catalyst compositions produced in Examples 3 to 10, 0.10 g of diisobutylaluminum hydride was added as a molecular weight modifier. When using the catalyst compositions produced in Examples 1, 2, Comparative Example 1, and Comparative Example 2, 0.25 g of diisobutylaluminum hydride was added as a molecular weight modifier. After adding the catalyst compositions produced in Examples 1 to 10 and Comparative Examples 1 and 2, polymerization was carried out. When the polymerization conversion rate reached 98% or higher, an n-hexane solution containing 1.0 g of polymerization inhibitor and a solution in which the antioxidant Irganox 1520 (BASF) was dissolved at 30% by weight in n-hexane were added to terminate the reaction. The resulting polymer was placed in steam-heated hot water and stirred. After removing the solvent, it was roll-dried to remove the remaining solvent and water, and a butadiene polymer was produced.

[0147] During the production of the butadiene polymer, a portion of the polymerization solution was taken after 25 minutes of reaction time following the start of polymerization, and the TSC (total solid contents, %) was measured. The polymerization conversion rate was then calculated using the following formula 1. The polymerization conversion rate after 25 minutes of reaction time was measured for each catalyst composition in Examples 1 to 10 and Comparative Examples 1 and 2 to evaluate the activity of the catalyst compositions, which are shown in Table 1 below. The measured value for Comparative Example 1 was used as the baseline value, and the activity of the catalyst compositions in each example and comparative example was indexed using the following formula 2. Furthermore, the properties of the catalyst compositions produced in Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated visually, and their forms are shown in Tables 1 and 2 below.

[0148] [Formula 1] Polymerization conversion rate (%) = TSC of the sample (%) / Concentration of 1,3-butadiene added (wt%) [Formula 2] Activity Index = (Measured Value / Reference Value) × 100

[0149] [Table 1]

[0150] [Table 2]

[0151] As shown in Tables 1 and 2 above, the catalyst compositions produced in Examples 1 to 10 were confirmed to be clear liquid catalysts, and their activity was significantly higher than that of Comparative Examples 1 and 2.

[0152] In particular, it was confirmed that the activity of the catalyst compositions produced in Examples 3 to 10 was further improved by performing a pretreatment step prior to the alkylation reaction with lanthanum-based rare earth element compounds.

[0153] In contrast, in Comparative Examples 1 and 2, in which the pretreatment step using tri-n-hexylaluminum and tri-n-octylaluminum was not performed on the lanthanum-based rare earth element compound according to the present invention, it was confirmed that the activity of the catalyst composition decreased. In particular, in Comparative Example 1, it was directly confirmed that the activity of the catalyst composition decreased compared to Examples 1-3, 5, 7, and 9, which used the same alkylating agent and halide. Similarly, in Comparative Example 2, it was directly confirmed that the activity of the catalyst composition decreased compared to Examples 4 and 8, which used the same alkylating agent and halide.

[0154] Experimental Example 2: Evaluation of the physical properties of conjugated diene polymers The Mooney viscosity, molecular weight distribution, and cis-1,4 bond content of the conjugated diene polymer produced in Experimental Example 1 using the catalyst compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were measured as follows and are shown in Tables 3 and 4 below.

[0155] *Mooney viscosity (ML1+4, @100℃): For each polymer, the Mooney viscosity was measured using a Monsanto MV2000E Large Rotor at 100℃ and a Rotor Speed ​​of 2±0.02 rpm. The sample used was left at room temperature (23±3℃) for at least 30 minutes, then 27±3g was taken and placed inside the die cavity. The platen was then operated, and the Mooney viscosity was measured while applying torque.

[0156] *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, and then loaded into a gel permeation chromatography (GPC) system. The columns used were a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories. Newly replaced columns were all mixed-bed type columns, and polystyrene was used as the GPC standard material.

[0157] *Cis-1,4 bond content: The cis-1,4 bond content of the conjugated diene was measured by Fourier transform infrared spectroscopy (FT-IR). Specifically, the FT-IR transmittance spectrum of a carbon disulfide solution of the conjugated diene polymer, prepared at a concentration of 5 mg / mL using carbon disulfide from the same cell as a blank, was measured, and the 1130 cm⁻¹ of the measured spectrum was then measured. -1 The maximum peak value in the vicinity (a, baseline), 967 cm², indicating trans-1,4 coupling. -1 The smallest peak value in the vicinity (b), 911 cm², indicating vinyl bonding. -1 The minimum peak value in the vicinity (c), and 736 cm², which indicates cis-1,4 bonding. -1 The respective contents were determined using the nearest minimum peak value (d).

[0158] [Table 3]

[0159] [Table 4]

[0160] As shown in Tables 3 and 4 above, the conjugated diene polymers produced using the catalyst compositions manufactured in Examples 1 to 10 exhibited a moderate level of Mooney viscosity and ensured a high level of cis-1,4 bond content. In particular, the conjugated diene polymers produced using the catalyst compositions manufactured in Examples 3, 4, 6 to 8, and 10 were found to be excellent in terms of Mooney viscosity, molecular weight distribution, and cis-1,4 bond content.

[0161] In contrast, the conjugated diene polymers produced using the catalyst compositions manufactured in Comparative Examples 1 and 2 exhibited a broad molecular weight distribution, and it was confirmed that the cis-1,4 bond content was lower compared to Examples 3, 4, 6-8, and 10.

[0162] Experimental Example 3: Evaluation of the physical properties of rubber compositions After producing rubber compositions and rubber test pieces using the conjugated diene polymer produced in Experimental Example 1 with the catalyst compositions of Examples 1 to 10 and Comparative Examples 1 and 2, the Mooney viscosity, abrasion resistance, tensile properties, and viscoelastic properties of the rubber compositions were measured using the following methods and are shown in Tables 5 and 6 below.

[0163] <Manufacturing of rubber compositions and rubber test specimens> Each of the catalyst compositions of Examples 1 to 10 and Comparative Examples 1 and 2 was used to produce the conjugated diene polymer produced in Experimental Example 1, to which 100 parts by weight was blended with 70 parts by weight of carbon black, 22.5 parts by weight of process oil (TDAE oil), 2 parts by weight of an antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO), and 2 parts by weight of stearic acid.

[0164] Subsequently, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), and 0.5 parts by weight of vulcanization accelerator (DPG) were added to each of the rubber compositions, and the mixture was weakly mixed at 50 rpm for 1 minute and 30 seconds at 50°C. Then, a sheet-like vulcanized compound was produced using a roll at 50°C, and the vulcanized compound was vulcanized at 160°C for 25 minutes to produce rubber test pieces.

[0165] *Tensile properties: After vulcanizing each rubber composition produced above at 150°C for 90 minutes, the modulus of the vulcanized product at 300% elongation (M-300%, kg·f / cm²) was determined according to ASTM D412. 2 The following values ​​were measured. The measured value of Comparative Example 1 was used as the reference value, and the 300% modulus of each example and comparative example was indexed using the following formula 3. [Formula 3] M-300% Index = (Measured value / Reference value) × 100

[0166] *Viscoelastic properties: Using a DMTS 500N from Gabo GmbH, Germany, the viscoelastic coefficient (Tanδ) was measured at a frequency of 10 Hz, with a prestrain of 3% and a dynamic strain of 3%, from -60°C to 60°C. In this case, the Tanδ value at 0°C indicates road surface resistance, and the Tanδ value at 60°C indicates rolling resistance characteristics (fuel efficiency). The measured value of Comparative Example 1 was used as the reference value, and the viscoelastic properties of each example and comparative example were indexed using the following formula 4. [Formula 4] Tanδ 60℃ Index = (Reference value / Measured value) × 100

[0167] *Abrasion resistance: Each rubber test piece manufactured as described above was subjected to a DIN abrasion test in accordance with ASTM D5963, and the results were expressed as the DIN wt loss index (loss volume index: ARIA (Abrasion resistance index, Method A)). The measured value of Comparative Example 1 was used as the reference value, and the abrasion resistance of each example and comparative example was indexed using the following formula 5. [Formula 5] Wear Index = (Reference Value / Measured Value) × 100

[0168] [Table 5]

[0169] [Table 6]

[0170] As shown in Tables 5 and 6 above, it was confirmed that the rubber compositions produced using the catalyst compositions manufactured in Examples 1 to 10, and containing the conjugated diene polymer, exhibited improved tensile properties, viscoelastic properties, and abrasion resistance compared to the rubber composition produced using the catalyst composition manufactured in Comparative Example 1. In particular, it was confirmed that the rubber compositions produced using the catalyst compositions manufactured in Examples 3 to 10, and containing the conjugated diene polymer, exhibited significantly improved tensile properties, viscoelastic properties, and abrasion resistance.

[0171] In contrast, it was confirmed that the rubber composition produced using the catalyst composition produced in Comparative Example 2, which contained a conjugated diene polymer, exhibited lower tensile properties, viscoelastic properties, and abrasion resistance compared to the rubber composition produced using the catalyst composition produced in Comparative Example 1.

[0172] These results are attributed to the fact that, during the preparation of catalyst compositions for producing conjugated diene polymers, the catalytic activity was improved by pre-treating hydrogen-bonded lanthanum rare earth element compounds and / or oligomeric forms of lanthanum rare earth element compounds, which cause a decrease in catalytic activity, either prior to or simultaneously with the alkylation reaction.

[0173] These results confirm that the catalyst composition produced by the method for producing the catalyst composition of the present invention exhibits excellent catalytic activity when pre-treated with hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomeric forms of lanthanum-based rare earth element compounds, which cause a decrease in catalytic activity, prior to or simultaneously with the alkylation reaction.

[0174] Furthermore, it was confirmed that the conjugated diene polymer produced by the method for producing conjugated diene polymers of the present invention exhibits high catalytic activity, resulting in a low content of residual lanthanum rare earth elements, high cis bond content and linearity, a narrow molecular weight distribution, and excellent abrasion resistance and low fuel consumption when applied to rubber compositions.

Claims

1. The alkylation reaction step (S10) involves mixing a lanthanum-based rare earth element compound with an alkylating agent and reacting them, The halogenation reaction step (S20) involves mixing the alkylated lanthanum-based rare earth element compound and the halide in step (S10) and reacting them, Includes, The (S10) step is carried out including a pretreatment agent, or The lanthanum-based rare earth element compound in step (S10) is a lanthanum-based rare earth element compound that has been pretreated by a pretreatment step (S1) in which hydrogen bonding, oligomerization, or a combination thereof is performed on the lanthanum-based rare earth element compound, thereby achieving hydrogen bonding, oligomerization, or a combination thereof. The aforementioned pretreatment agent is one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum. The (S1) step is a method for producing a catalyst composition, wherein the step is carried out by mixing and reacting a lanthanum-based rare earth element compound with one or more trialkylaluminum selected from the group consisting of tri-n-hexylaluminum and tri-n-octylaluminum.

2. The method for producing the catalyst composition according to claim 1, wherein step (S1) is performed before the alkylation reaction with trialkylaluminum occurs with the lanthanum-based rare earth element compound.

3. The method for producing the catalyst composition according to claim 1, wherein the lanthanum-based rare earth element compound is a neodymium compound represented by the following chemical formula 1. 【Chemistry 1】 In the aforementioned chemical formula 1, R １ ~R ３ Each is independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R １ ~R ３ Not all of it is hydrogen.

4. The lanthanum-based rare earth element compound is Nd(2-ethylhexanoate). ３ , Nd(2,2-dimethyldecanoate). ３ , Nd(2,2-diethyldecanoate). ３ , Nd(2,2-dipropyldecanoate). ３ , Nd(2,2-dibutyldecanoate). ３ , Nd(2,2-dihexyldecanoate). ３ , Nd(2,2-dioctyldecanoate). ３ , Nd(2-ethyl-2-propyldecanoate). ３ , Nd(2-ethyl-2-butyldecanoate). ３ , Nd(2-ethyl-2-hexyldecanoate). ３ , Nd(2-propyl-2-butyldecanoate). ３ , Nd(2-propyl-2-hexyldecanoate). ３ , Nd(2-propyl-2-isopropyldecanoate). ３ , Nd(2-butyl-2-hexyldecanoate). ３ , Nd(2-hexyl-2-octyldecanoate). ３ , Nd(2,2-diethyloctanoate). ３ , Nd(2,2-dipropyloctanoate). ３ , Nd(2,2-dibutyloctanoate). ３ , Nd(2,2-dihexyloctanoate). ３ , Nd(2-ethyl-2-propyloctanoate). ３ , Nd(2-ethyl-2-hexyloctanoate). ３ , Nd(2,2-diethylnonanoate). ３ , Nd(2,2-dipropylnonanoate). ３ , Nd(2,2-dibutylnonanoate). ３ , Nd(2,2-dihexylnonanoate). ３ , Nd(2-ethyl-2-propylnonanoate). ３ , and Nd(2-ethyl-2-hexylnonanoate). ３ The method for producing the catalyst composition according to claim 1, which is one or more selected from the group consisting of.

5. The method for producing the catalyst composition according to claim 1, wherein the alkylating agent is an alkylaluminum compound represented by the following chemical formula 2. [Chemical formula 2] AlR ４ R ５ R ６ In the aforementioned chemical formula 2, R ４ ~R ６ Each is independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ４ ~R ６ It is not entirely hydrogen, and does not contain tri-n-hexylaluminum or tri-n-octylaluminum.

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

7. A method for producing a catalyst composition according to claim 1, wherein the pretreatment reaction in step (S1), the alkylation reaction in step (S10), or the pretreatment reaction in step (S1) and the alkylation reaction in step (S10) are carried out using a conjugated diene monomer.

8. The method for producing the catalyst composition according to claim 1, wherein the halogen is one or more selected from the group consisting of alkylaluminum halides represented by the following chemical formula 3 and alkylaluminum sesquihalides represented by the following chemical formula 4. [Chemical formula 3] AlR ７ R ８ R ９ In the aforementioned chemical formula 3, R ７ ~R ９ Each of these is independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R ７ ~R ９ Not all of them are halogen groups. 【Chemistry 2】 In the aforementioned chemical formula 4, R １０ ~R １２ Each of these is independently an alkyl group having 1 to 12 carbon atoms. X １ ~X ３ Each of these is independently a halogen group.

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

10. A method for producing a conjugated diene polymer, comprising the step (S100) of polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition produced by the method for producing a catalyst composition described in claim 1, in order to produce an active polymer.

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