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

Abstract

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

Description

[Technical field]

[0001] The present invention claims the benefit of priority based on Korean Patent Application No. 10-2022-0021074, filed on February 17, 2022, and all contents disclosed in the documents of the Korean patent application are incorporated as part of this specification.

[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, there has been growing interest in energy conservation and environmental issues, and this has led to a demand for improved fuel efficiency in automobiles. As one method for achieving this, a method has been proposed in which the cis bond content and linearity of polybutadiene in a rubber composition for forming tires are increased while the molecular weight distribution is narrowed.

[0004] Polybutadiene is produced using Ziegler-Natta catalysts, which are produced by activating an organic acid metal compound with an alkylaluminum and an alkylaluminum halide compound, and then reacting the produced catalyst with 1,3-butadiene monomer to produce polybutadiene.

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

[0006] Representative examples of the lanthanum-based rare earth element compounds include neodymium-based compounds, and a specific example is NdV (neodymium versatate), etc. These are activated through alkylation using an alkylaluminum compound and then halogenation using an alkylaluminum halide compound, and in order to stabilize the catalyst, 1,3-butadiene monomer may be added during the alkylation reaction to perform preforming.

[0007] In this case, lanthanum rare earth compounds such as NdV do not exist in the form of a single compound, but in the form of hydrogen bonds and / or oligomers formed by moisture and aliphatic compounds used in the manufacturing process (Non-Patent Documents 1 and 2). However, when alkylation is immediately performed on hydrogen-bonded lanthanum rare earth compounds and / or oligomers of lanthanum rare earth compounds, the alkylation takes a long time compared to when the lanthanum rare earth compounds are in the form of a single compound, and the alkylation reaction does not proceed sufficiently. When such a lanthanum rare earth compound that has not been sufficiently alkylated is introduced into a halogenation reactor for halogenation, it causes a decrease in catalyst activity and increases contamination of the catalyst manufacturing equipment.

[0008] US Patent Registration No. 9056303 (Patent Document 1) discloses a method for producing a catalyst system using multiple alkylation reactors. Patent Document 1 is characterized in that, when producing a catalyst system continuously in order to eliminate the drawbacks of producing the catalyst system in a batch mode, the type of reactor is specifically specified to prevent gel formation in the reactor and ensure the flexibility of the alkylating agent and rare earth salt that affect the catalyst activity, and the flow rate of the outlet of the catalyst system at the line outlet is adjusted as necessary to remain within a suitable residence time range for the alkylation reaction and the chlorination reaction. In addition, Japanese Patent Registration No. 5072191 (Patent Document 2) discloses a method for producing a catalyst for conjugated diene polymerization in which an alkylaluminum compound and an alkylaluminum hydride for the alkylation reaction are sequentially charged. However, Patent Documents 1 and 2 only directly perform an alkylation reaction on a lanthanum compound during the production of the catalyst system and the catalyst for conjugated diene polymerization, and do not recognize the form of the lanthanum compound charged during the alkylation reaction and its effect on the catalyst activity. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] US9056303B2 [Patent Document 2] JP5072191B2 [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) Summary of the Invention [Problem to be solved by the invention]

[0011] The problem to be solved by the present invention is to improve the catalytic activity of a catalyst composition for the polymerization of polybutadiene by pretreating hydrogen-bonded lanthanum rare earth compounds and / or oligomer forms of lanthanum rare earth compounds, which cause a decrease in catalytic activity, prior to an alkylation reaction.

[0012] That is, in order to solve the problems mentioned in the Background of the Invention, the present invention aims to provide a method for preparing a catalyst composition having improved catalytic activity by pretreating hydrogen-bonded lanthanum rare earth compounds and / or oligomeric forms of lanthanum rare earth compounds, which cause a decrease in catalytic activity.

[0013] Another object of the present invention is to provide a method for producing a conjugated diene-based polymer having a high cis-bond content and linearity and a narrow molecular weight distribution, by using a catalyst composition produced by the method for producing a catalyst composition. [Means for solving the problem]

[0014] In order to solve the above problems, the present invention provides a method for producing a catalyst composition and a method for producing a conjugated diene-based polymer.

[0015] (1) The present invention provides a method for producing a catalyst composition, comprising: a pretreatment step (S10) of performing a pretreatment reaction on a hydrogen bond, oligomer form, or a combination thereof of a lanthanum rare earth compound; an alkylation reaction step (S20) of mixing and reacting the lanthanum rare earth compound pretreated in the hydrogen bond, oligomer form, or combination thereof in the (S10) step with an alkylating agent; and a halogenation reaction step (S30) of mixing and reacting the lanthanum rare earth compound alkylated in the (S20) step with a halide.

[0016] (2) The present invention provides a method for producing the catalyst composition according to (1) above, wherein the (S10) step is carried out by mixing and reacting a lanthanum rare earth compound with one or more trialkylaluminums selected from the group consisting of trimethylaluminum and triethylaluminum.

[0017] (3) The present invention provides a method for producing a catalyst composition according to (2) above, wherein the step (S10) is carried out before the alkylation reaction of the lanthanum rare earth compound with trialkylaluminum occurs.

[0018] (4) The present invention provides a method for producing a catalyst composition according to any one of (1) to (3) above, wherein the lanthanum rare earth element compound is a neodymium compound represented by the following chemical formula 1:

[0019] [ka]

[0020] In the above formula 1, R 1 ~R 3 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 1 ~R 3 cannot all be hydrogen.

[0021] (5) The present invention relates to a lanthanum rare earth compound, and the lanthanum rare earth 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-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd( ... Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate The present invention provides a method for producing the catalyst composition according to any one of (1) to (4), wherein the 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.

[0022] (6) The present invention provides a method for producing a catalyst composition according to any one of (1) to (5) above, wherein the alkylating agent is an alkylaluminum compound represented by the following chemical formula 2:

[0023] [Chemical formula 2] AlR 4 R 5 R 6

[0024] In the above formula 2, R 4 ~R 6are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 4 ~R 6 Not all of R are hydrogen. 4 ~R 6 When all of are alkyl groups, the alkyl groups have 3 to 12 carbon atoms.

[0025] (7) The present invention provides a method for producing a catalyst composition according to any one of (1) to (6) above, wherein the alkylating agent is a dialkylaluminum hydride.

[0026] (8) The present invention provides a method for producing a catalyst composition according to any one of (1) to (7), wherein the pretreatment reaction in step (S10), the alkylation reaction in step (S20), or the pretreatment reaction in step (S10) and the alkylation reaction in step (S20) are carried out using a conjugated diene monomer.

[0027] (9) The present invention provides a method for producing a catalyst composition according to any one of (1) to (8) above, wherein the halide is at least one 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:

[0028] [Chemical formula 3] AlR 7 R 8 R 9

[0029] In the above formula 3, R 7 ~R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R 7 ~R 9 Not all of the groups are halogen groups,

[0030] [ka]

[0031] In the above Chemical Formula 4, R 10 ~R 12 are each independently an alkyl group having 1 to 12 carbon atoms, and X1 to X3 are each independently a halogen group.

[0032] (10) The present invention provides a method for producing a catalyst composition according to any one of (1) to (9) above, wherein the halide is at least one selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides.

[0033] (11) The present invention provides a method for producing a conjugated diene polymer, comprising a 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 according to any one of (1) to (10) above to produce an active polymer.

[0034] (12) The present invention provides a conjugated diene polymer produced by the method for producing a conjugated diene polymer according to (11) above.

[0035] (13) The present invention provides a rubber composition containing the conjugated diene polymer described in (12) above. Effect of the Invention

[0036] The catalyst composition produced by the method for producing a catalyst composition of the present invention has excellent catalytic activity because it is produced by pretreating hydrogen-bonded lanthanum rare earth compounds and / or oligomer forms of lanthanum rare earth compounds, which cause a decrease in catalytic activity, prior to an alkylation reaction.

[0037] The conjugated diene polymer produced by the method for producing a conjugated diene polymer of the present invention has a low content of lanthanum-based rare earth elements remaining in the conjugated diene polymer due to its high catalytic activity, a high content and linearity of cis bonds, and a narrow molecular weight distribution, and when applied to a rubber composition, it exhibits excellent wear resistance and fuel economy. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0038] The present invention will now be described in more detail so that the present invention may be easily understood.

[0039] The terms and words used in the description of the present invention and the claims should not be interpreted in a limited manner to their ordinary or dictionary meanings, but should be interpreted in a manner that is consistent with the technical idea of ​​the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0040] Method for producing catalyst composition The present invention provides a method for producing a catalyst composition. The catalyst composition produced by the method for producing a catalyst composition may be a catalyst composition for polymerization of a conjugated diene-based polymer.

[0041] According to one embodiment of the present invention, the method for preparing the catalyst composition may include a pretreatment step (S10) of performing a pretreatment reaction on a hydrogen-bonded, oligomeric, or combination thereof lanthanum rare earth compound, an alkylation reaction step (S20) of mixing and reacting the lanthanum rare earth compound pretreated in the hydrogen-bonded, oligomeric, or combination thereof in the step (S10) with an alkylating agent, and a halogenation reaction step (S30) of mixing and reacting the lanthanum rare earth compound alkylated in the step (S20) with a halide.

[0042] As described in the Background Art of the present invention, lanthanum rare earth compounds do not exist in the form of a single compound, but in the form of hydrogen bonds and / or oligomers formed by moisture and aliphatic compounds used in the manufacturing process (see Non-Patent Documents 1 and 2). However, when the hydrogen-bonded lanthanum rare earth compounds and / or oligomers of lanthanum rare earth compounds are directly alkylated, the alkylation takes a long time compared to when the lanthanum rare earth compounds are in the form of a single compound, and the alkylation reaction does not proceed sufficiently. When the lanthanum rare earth compounds that have not been sufficiently alkylated are introduced into a halogenation reactor for carrying out the halogenation reaction, this causes a decrease in the activity of the catalyst and also causes a problem of increasing contamination of the catalyst manufacturing equipment. However, in the manufacturing method of the catalyst composition according to the present invention, the hydrogen-bonded lanthanum rare earth compounds and / or oligomers of lanthanum rare earth compounds are pretreated before the alkylation reaction in the step (S10), thereby improving the catalytic activity. Here, the pretreatment means minimizing or even removing hydrogen-bonded lanthanum rare earth compounds and / or oligomeric forms of lanthanum rare earth compounds prior to the alkylation reaction.

[0043] According to one embodiment of the present invention, the step (S10) may be performed by mixing and reacting the lanthanum rare earth compound with one or more trialkylaluminums selected from the group consisting of trimethylaluminum and triethylaluminum. It is known that the trimethylaluminum and triethylaluminum can be used as alkylating agents in the alkylation reaction. However, when the trimethylaluminum and triethylaluminum are used simply as alkylating agents, rather than for the pretreatment reaction in the step (S10) of the present invention, the alkylation reaction of the lanthanum rare earth compound can only be induced according to the purpose, which causes a problem that the alkylation reaction takes a long time and does not proceed sufficiently. From this point of view, the step (S10) may be performed before the alkylation reaction of the lanthanum rare earth compound with one or more trialkylaluminums selected from the group consisting of trimethylaluminum and triethylaluminum occurs. Meanwhile, trialkylaluminum and / or dialkylaluminum hydrides usable as alkylating agents other than trimethylaluminum and triethylaluminum cannot sufficiently induce a pretreatment reaction on the hydrogen bond, oligomer form, or a combination thereof of the lanthanum rare earth compound, and are therefore not suitable as trialkylaluminum compounds for the pretreatment reaction in the (S10) step.

[0044] According to one embodiment of the present invention, the step (S10) may be performed by adding one or more trialkylaluminums selected from the group consisting of trimethylaluminum and triethylaluminum in a molar ratio of 1 mol or more, 2 mol or more, 3 mol or more, 4 mol or more, 5 mol or more, 6 mol or more, 7 mol or more, 8 mol or more, 9 mol or more, or 10 mol or more, or 20 mol or less, 19 mol or less, 18 mol or less, 17 mol or less, 16 mol or less, 15 mol or less, 14 mol or less, 13 mol or less, 12 mol or less, 11 mol or less, or 10 mol or less, relative to 1 mol of the lanthanum rare earth compound.

[0045] According to one embodiment of the present invention, the (S10) step may be performed at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, and may be performed at a temperature of 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, or 20°C or lower.

[0046] According to one embodiment of the present invention, the (S10) step 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 be performed for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0047] According to one embodiment of the present invention, in step (S10), the efficiency of the pretreatment reaction performed on the hydrogen bond, oligomer form, or a combination thereof of the lanthanum rare earth compound can be further improved by adjusting the molar ratio of the lanthanum rare earth compound to one or more trialkylaluminums selected from the group consisting of trimethylaluminum and triethylaluminum, the reaction temperature, and the reaction time.

[0048] According to an embodiment of the present invention, the lanthanum rare earth compound may be a neodymium compound, and specific examples thereof include neodymium carboxylates (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.); organic phosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, etc.); phosphates, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl)phosphate, neodymium bis(2-ethylhexyl)phosphate, or neodymium didecyl phosphate; 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 neodymium dodecylphosphonate, or neodymium octadecylphosphonate; organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl)phosphinate, or neodymium (2-ethylhexyl)phosphinate); carbamates (e.g., neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate); , neodymium dibutylcarbamate, or neodymium dibenzylcarbamate; dithiocarbamates (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, or neodymium dibutyldithiocarbamate); xanthogenates (e.g., neodymium methylxanthogenate, neodymium ethylxanthogenate, neodymium isopropylxanthogenate, neodymium butylxanthogenate, or neodymium benzylxanthogenate);β-diketonates (such as neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, or neodymium benzoylacetonate); alkoxides or aryloxides (such as neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide, or neodymium nonylphenoxide); halides or pseudohalides (such as neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide, etc.); oxyhalides (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide, etc.); or organic neodymium compounds containing one or more rare earth element-carbon bonds (e.g., Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, or Ln(allyl)2Cl, etc., where Ln is a rare earth metal element and R is a hydrocarbyl group), and the like, which may include any one or a mixture of two or more of these;

[0049] According to an embodiment of the present invention, the lanthanide rare earth compound may be a neodymium compound represented by the following Chemical Formula 1:

[0050] [ka]

[0051] In the above formula 1, R 1 ~R 3 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 1 ~R 3 Not all of R are hydrogen. 1 is an alkyl group having 4 to 12 carbon atoms, and R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 2 to 8 carbon atoms; R 2 and R3 Not all of R are hydrogen. 1 is an alkyl group having 6 to 8 carbon atoms, and R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 2 to 6 carbon atoms; R 2 and R 3 cannot all be hydrogen.

[0052] According to one embodiment of the present invention, the lanthanum rare earth compound is Nd(2-ethylhexanoate)3 (neodymium versatate), Nd(2,2-dimethyldecanoate)3, Nd(2,2-diethyldecanoate)3, Nd(2,2-dipropyldecanoate)3, Nd(2,2-dibutyldecanoate)3, Nd(2,2-dihexyldecanoate)3, Nd(2 ,2-dioctyldecanoate)3, Nd(2-ethyl-2-propyldecanoate)3, Nd(2-ethyl-2-butyldecanoate)3, Nd(2-ethyl-2-hexyldecanoate)3, Nd(2-propyl-2-butyldecanoate)3, Nd(2-propyl-2-hexyldecanoate)3, Nd(2-propyl-2-isopropyldecanoate)3, Nd(2 -butyl-2-hexyldecanoate)3, Nd(2-hexyl-2-octyldecanoate)3, Nd(2,2-diethyloctanoate)3, Nd(2,2-dipropyloctanoate)3, Nd(2,2-dibutyloctanoate)3, Nd(2,2-dihexyloctanoate)3, Nd(2-ethyl-2-propyloctanoate)3, Nd(2-ethyl-2- The compound may be one or more selected from the group consisting of 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.

[0053] According to one embodiment of the present invention, the neodymium compound contains a carboxylate ligand containing an alkyl group of various lengths having 2 or more carbon atoms as a substituent at the α-position, which induces a three-dimensional change around the central metal of neodymium and can block the phenomenon of entanglement between compounds, thereby suppressing oligomerization during polymerization of a conjugated diene polymer using the catalyst composition. In addition, such a neodymium-based compound has a high solubility in a solvent, and the proportion of neodymium located in the central portion, which is difficult to convert to catalytically active species, is reduced, resulting in a high conversion rate to catalytically active species.

[0054] 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 the non-polar solvent at room temperature (25° C.). The solubility of the neodymium-based compound means the degree to which the compound is dissolved cleanly without becoming cloudy. Such high solubility allows the compound to exhibit excellent catalytic activity.

[0055] According to one embodiment of the present invention, the step (S10) may be carried out by including a conjugated diene monomer. This is to form a pre-polymerized or premixed catalyst composition by pre-mixing a conjugated diene monomer used in the polymerization reaction of a conjugated diene polymer using the catalyst composition prepared according to the present invention with the catalyst composition, which can further improve the activity of the catalyst composition and stabilize the active polymer produced. The "pre-polymerization" 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., in order to reduce the possibility of generating active species of various catalyst compositions in the catalyst system, and pre-polymerization is performed in the catalyst composition system together with the addition of 1,3-butadiene. Also, "premix" may mean a state in which polymerization is not performed in the catalyst composition system and each compound is uniformly mixed.

[0056] According to one embodiment of the present invention, the conjugated diene monomer that can be added in step (S10) 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 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.

[0057] According to an embodiment of the present invention, when the 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 the lanthanum rare earth compound, or 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.

[0058] According to one embodiment of the present invention, step (S20) is a step for performing an alkylation reaction on a lanthanum rare earth compound, and may be performed by mixing and reacting the lanthanum rare earth compound that has been pretreated in step (S10) for hydrogen bonding, oligomer form, or a combination thereof with an alkylating agent.

[0059] According to one embodiment of the present invention, the alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and can act as a cocatalyst. 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.

[0060] According to one embodiment of the present invention, the alkylating agent may be an organoaluminum compound, and specific examples thereof include 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. aluminum hydride, dihydrocarbyl aluminum hydrides such as phenyl-n-octylaluminum 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-octylaluminum hydride, benzylethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzylisopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzylisobutyl aluminum hydride, or benzyl-n-octylaluminum hydride; hydrocarbyl aluminum dihydrides such as ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride, or n-octylaluminum dihydride, etc.

[0061] According to one embodiment of the present invention, the alkylating agent is preferably an alkylaluminum compound in terms of controlling catalytic reactions and side reactions caused by the lanthanum rare earth element compound pretreated in step (S10) for hydrogen bonding, oligomer form, or a combination thereof. As a specific example, the alkylating agent may be an alkylaluminum compound represented by the following formula 2:

[0062] [Chemical formula 2] AlR 4 R 5 R 6

[0063] In the above formula 2, R 4 ~R 6 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 4 ~R 6 Not all of R are hydrogen. 4 ~R 6 When all of R are alkyl groups, the number of carbon atoms in the alkyl group may be 3 to 12. 4 ~R 6 are each independently a hydrogen atom or an alkyl group having 3 to 8 carbon atoms; R 4 ~R 6 Not all of R are hydrogen. 4 ~R 6 When all of R are alkyl groups, the number of carbon atoms in the alkyl group may be 3 to 6. As a more specific example, in the above Chemical Formula 2, R 4 ~R 6 are each independently a hydrogen atom or an alkyl group having 3 to 6 carbon atoms; R 4 ~R 6 cannot all be hydrogen.

[0064] According to one embodiment of the present invention, the alkylating agent may be a dialkylaluminum hydride from the viewpoint of controlling catalytic reactions and side reactions caused by the lanthanum rare earth compound pretreated in step (S10) for hydrogen bonding, oligomer form, or a combination thereof, and the type of dialkylaluminum hydride is as described above. As a specific example, the alkylating agent may be diisobutylaluminum hydride.

[0065] According to one embodiment of the present invention, the alkylating agent may include two or more alkylaluminum compounds. As a specific example, the alkylating agent may include two or more selected from the group consisting of dialkylaluminum hydride and trialkylaluminum. As a more specific example, the alkylating agent may include one or more dialkylaluminum hydrides and one or more trialkylaluminums, and as a further specific example, the alkylating agent may include diisobutylaluminum hydride and triisobutylaluminum.

[0066] According to one embodiment of the present invention, the (S20) step may be performed 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, or 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, 20 moles or less, 19 moles or less, 18 moles or less, 17 moles or less, 16 moles or less, or 15 moles or less, based on 1 mole of the lanthanum rare earth compound pretreated in the (S10) step for hydrogen bonding, oligomer form, or a combination thereof.

[0067] According to one embodiment of the present invention, the (S20) step may be performed at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, and may be performed at a temperature of 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, or 20°C or lower.

[0068] According to one embodiment of the present invention, the (S20) step 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 be performed for 2 hours or less, 1 hour and 30 minutes or less, 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0069] According to one embodiment of the present invention, in step (S20), the catalytic activity can be further improved by adjusting the molar ratio of the lanthanum rare earth compound pretreated in step (S10) for hydrogen bonding, oligomer form, or a combination thereof to the alkylating agent, the reaction temperature, and the reaction time.

[0070] According to one embodiment of the present invention, the step (S20) may be carried out using a conjugated diene monomer for the same purpose as the step (S10). In this case, when the step (S20) is carried out using a conjugated diene monomer, the step (S20) may be carried out using a conjugated diene monomer separately from or simultaneously with the step (S10).

[0071] According to an embodiment of the present invention, when the step (S20) is carried out including a conjugated diene monomer, the conjugated diene monomer may be added in a molar ratio of 1 mol or more, 5 mol or more, 10 mol or more, 15 mol or more, or 20 mol or more, or 100 mol or less, 90 mol or less, 80 mol or less, 70 mol or less, 60 mol or less, or 50 mol or less, per mol of the lanthanum rare earth compound pretreated in the step (S10) for hydrogen bonding, oligomer form, or a combination thereof.

[0072] According to an embodiment of the present invention, step (S30) is a step for performing a halogenation reaction on the lanthanum rare earth compound alkylated in step (S20), and may be performed by mixing and reacting the lanthanum rare earth compound alkylated in step (S20) with a halide.

[0073] According to an embodiment of the present invention, the halide may be a halogen, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometal halide.

[0074] According to one embodiment of the present invention, the halogen element may be fluorine, chlorine, bromine, or iodine.

[0075] According to an embodiment of the present invention, the interhalogen compound may be iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, or iodine trifluoride, etc.

[0076] According to one embodiment of the present invention, the hydrogen halide may be hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide.

[0077] According to one embodiment of the present invention, the organic halide is t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methylchloroformate, methylbromoformate, iodomethane, diiodomethane, triiodomethane (also called "iodoform"). iodide), 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"), trimethylsilyliodide, triethylsilyliodide, triphenylsilyliodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, or methyl iodoformate.

[0078] According to one embodiment of the present invention, the non-metal halide may be phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl4), silicon tetrabromide, arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide, or selenium tetraiodide, etc.

[0079] According to an 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, etc.

[0080] According to an embodiment of the present invention, the organometallic halide may be an alkylaluminum halide or an alkylaluminum sesquihalide. Specific examples of the organometallic halide include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, 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-butylsulfite ... dichloride, 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 diiodide, ethylaluminum diiodide, n-butylaluminum diiodide , isobutylaluminum 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.

[0081] According to one embodiment of the present invention, the halide may be at least one 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.

[0082] [Chemical formula 3] AlR 7 R 8 R 9

[0083] In the above formula 3, R 7 ~R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, and R 7 ~R 9 Not all of R are halogen groups. 7 ~R 9 are each independently a halogen group or an alkyl group having 1 to 6 carbon atoms, and R 7 ~R 9 Not all of R are halogen groups. 7 and R 8 are each independently an alkyl group having 1 to 4 carbon atoms; R 9 may be a halogen group.

[0084] [ka]

[0085] In the above Chemical Formula 4, R 10 ~R 12 may each independently be an alkyl group having 1 to 12 carbon atoms, and X1 to X3 may each independently be a halogen group. 10 ~R 12 may each independently be an alkyl group having 1 to 6 carbon atoms. 10 ~R 12may each independently be an alkyl group having 1 to 4 carbon atoms.

[0086] According to one embodiment of the present invention, the halide may be at least one selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides, from the viewpoint of controlling catalytic reactions and side reactions caused by the lanthanum rare earth compound pretreated in step (S10) for hydrogen bonding, oligomer form, or a combination thereof, and the types of dialkylaluminum halides and alkylaluminum sesquihalides are as described above. As a specific example, the dialkylaluminum halide may be diethylaluminum chloride, and the alkylaluminum sesquihalide may be ethylaluminum sesquichloride.

[0087] According to an embodiment of the present invention, the step (S30) may be performed by adding a molar ratio of 0.1 mol or more, 0.5 mol or more, 1.0 mol or more, 1.5 mol or more, 2.0 mol or more, 2.5 mol or more, or 3.0 mol or more of a halide relative to 1 mol of the lanthanum rare earth compound that has been pretreated in the step (S10) for hydrogen bonding, oligomerization, or a combination thereof, and may be performed by adding a molar ratio of 5.0 mol or less, 4.5 mol or less, 4.0 mol or less, 3.5 mol or less, or 3.0 mol or less.

[0088] According to one embodiment of the present invention, the (S30) step may be performed at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, and may be performed at a temperature of 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, or 20°C or lower.

[0089] According to one embodiment of the present invention, the (S30) step 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 be performed for 1 hour or less, 50 minutes or less, 40 minutes or less, or 30 minutes or less.

[0090] According to one embodiment of the present invention, in the step (S30), the catalytic activity can be further improved by adjusting the molar ratio of the lanthanum rare earth compound pretreated in the step (S10) for hydrogen bonding, oligomer form, or a combination thereof to the halide, the reaction temperature, and the reaction time.

[0091] According to an embodiment of the present invention, the steps (S10) to (S30) may be carried out in an organic solvent. The organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition. As a specific example, the organic solvent may be a linear, branched, or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms, such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isooctane, 2,2-dimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, or methylcyclohexane; a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether, petroleum spirits, or kerosene; or an aromatic hydrocarbon solvent, such as benzene, toluene, ethylbenzene, or xylene. As a more specific example, the organic solvent may be the linear, branched, or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, and preferably, n-hexane, cyclohexane, or a mixture thereof.

[0092] According to an embodiment of the present invention, steps (S10) to (S30) may be performed in a batch reactor, and steps (S10) to (S30) may be performed by sequentially adding the lanthanum rare earth compound, trialkylaluminum, alkylating agent, and halide for each step.

[0093] According to one embodiment of the present invention, all steps of the method for preparing the catalyst composition, including steps (S10) to (S30), may be performed at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, and may be performed at a temperature of 40°C or lower, 35°C or lower, 30°C or lower, 25°C or lower, 20°C or lower, or 15°C or lower.

[0094] According to one embodiment of the present invention, all steps of the method for preparing a catalyst composition including steps (S10) to (S30) may be performed for 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, or 70 minutes or more, and may be performed 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.

[0095] Method for producing conjugated diene polymer The present invention provides a method for producing a conjugated diene-based polymer.

[0096] According to an embodiment of the present invention, the method for producing a conjugated diene-based polymer may include a step (S100) of polymerizing a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a catalyst composition prepared by the method for preparing a catalyst composition to produce an activated polymer.

[0097] According to an embodiment of the present invention, the conjugated diene monomer that can be added in step (S100) may be at least one selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene.

[0098] According to one embodiment of the present invention, the hydrocarbon solvent in step (S100) may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0099] According to one embodiment of the present invention, the catalyst composition is a catalyst composition prepared by the above-mentioned method for preparing a catalyst composition, and the catalyst composition may be used in an amount of 0.03 mmol or more, 0.04 mmol or more, 0.05 mmol or more, or 0.06 mmol or more of the neodymium compound relative to a total of 100 g of the conjugated diene monomer, and may be used in an amount of 0.15 mmol or less, 0.14 mmol or less, 0.13 mmol or less, 0.12 mmol or less, 0.11 mmol or less, 0.10 mmol or less, 0.09 mmol or less, or 0.08 mmol or less.

[0100] According to one embodiment of the present invention, the polymerization in the step (S100) may be carried out by continuous polymerization in a polymerization reactor including at least two reactors, or may be carried out in a batch reactor, and may be temperature-rise polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization).

[0101] According to one embodiment of the present invention, the constant temperature polymerization refers to polymerization using the reaction heat of the catalyst composition itself without adding any heat after the catalyst composition is added, the temperature increasing polymerization refers to increasing the temperature by adding heat after the catalyst composition is added, and the isothermal polymerization refers to maintaining the temperature of the reactants constant by adding heat to increase the heat or removing heat after the catalyst composition is added.

[0102] According to one embodiment of the present invention, the polymerization in step (S100) may be carried out using coordination anion polymerization, and the polymerization environment may be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and a specific example may be solution polymerization.

[0103] According to an embodiment of the present invention, the polymerization in step (S100) may be performed at a temperature of -20° C. or more, -10° C. or more, 0° C. or more, 10° C. or more, 20° C. or more, 30° C. or more, 40° C. or more, 50° C. or more, or 60° C. or more, or at a temperature of 200° C. or less, 150° C. or less, 120° C. or less, or 90° C. or less. Within this range, the polymerization reaction can be smoothly controlled and the cis-1,4 bond content of the produced conjugated diene polymer can be ensured.

[0104] 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, and may be carried out for 3 hours or less, 2 hours and 30 minutes or less, or 2 hours or less.

[0105] According to an embodiment of the present invention, the conjugated diene-based polymer formed by polymerization in step (S100) may be an activated polymer including sites activated by the catalyst composition.

[0106] According to an embodiment of the present invention, the method may include reacting the activated polymer with a modifier (S200). The modifier may be a known modifier that can be used in the preparation of a conjugated diene-based polymer using a catalyst composition containing a lanthanum rare earth compound.

[0107] According to one embodiment of the present invention, the method for preparing the conjugated diene-based polymer may include a step of terminating the polymerization after preparing the activated polymer by further using an additive such as a reaction terminator for completing the polymerization reaction, such as polyoxyethylene glycol phosphate, or an antioxidant, such as 2,6-di-t-butyl-p-cresol, etc. In addition, an additive for facilitating solution polymerization, such as a chelating agent, a dispersing agent, a pH regulator, an oxygen scavenger, or an oxygen scavenger, may be selectively further used together with the reaction terminator.

[0108] Conjugated diene polymer The present invention provides a conjugated diene-based polymer.

[0109] According to an embodiment of the present invention, the conjugated diene-based polymer may be produced by the method for producing a conjugated diene-based polymer, i.e., the conjugated diene-based polymer may be polymerized in the presence of a catalyst composition produced by the method for producing a catalyst composition.

[0110] According to an embodiment of the present invention, the conjugated diene polymer may include a conjugated diene monomer unit. The conjugated diene monomer unit refers to a repeating unit formed by polymerization of a conjugated diene monomer.

[0111] According to an embodiment of the present invention, the conjugated diene-based polymer may contain 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or 100% by weight of 1,3-butadiene monomer units, and may selectively contain 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less of other conjugated diene-based monomer units copolymerizable with the 1,3-butadiene monomer. When the content is within this range, it is possible to prevent a decrease in the content of cis-1,4 bonds in the conjugated diene-based polymer. 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, and other conjugated diene monomers copolymerizable with the 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.

[0112] According to an embodiment of the present invention, the conjugated diene-based polymer may be a conjugated diene-based polymer catalyzed by a catalyst composition including a lanthanum rare earth element compound, i.e., the conjugated diene-based polymer may be a conjugated diene-based polymer including an organometallic moiety activated by a catalyst composition including a neodymium compound.

[0113] According to one embodiment of the present invention, the conjugated diene-based polymer has a weight average molecular weight (Mw) of 1.0×10 5 g / mol or more, 2.0X10 5 g / mol or more, 3.0X10 5 g / mol or more, 4.0X10 5 g / mol or more, 5.0X10 5 g / mol or more, 6.0X10 5 g / mol or more, 7.0X10 5 g / mol or more, 8.0X10 5 g / mol or more, or 9.0X10 5 g / mol or more, and 6 g / mol or less, 9.0X10 5 g / mol or less, 8.0X10 5 g / mol or less, 7.0X10 5 g / mol or less, 6.0X10 5 g / mol or less, 5.0X10 5 g / mol or less, 4.0X10 5 g / mol or less, or 3.0X10 5 The conjugated diene polymer may have a number average molecular weight (Mn) of 1.0×10 5 g / mol or more, 2.0X10 5 g / mol or more, 3.0X10 5 g / mol or more, 4.0X10 5 g / mol or more, or 5.0X10 5 g / mol or more, and 5 g / mol or less, 5.0X10 5 g / mol or less, 4.0X10 5 g / mol or less, 3.0X10 5 g / mol or less, 2.0X10 5 g / mol or less, or 1.0X10 5 Within this range, the rubber composition has excellent tensile properties when applied to the rubber composition, and has excellent processability to improve the workability of the rubber composition, making mixing and kneading easy, and has the effect of providing the rubber composition with excellent mechanical properties and balance of physical properties.

[0114] According to an embodiment of the present invention, the conjugated diene-based 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 be 4.0 or less, 3.5 or less, 3.0 or less, or 2.5 or less. The molecular weight distribution may be calculated from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In this case, the number average molecular weight (Mn) is a common average of molecular weights of individual polymers calculated by measuring the molecular weights of n polymer chains, calculating the sum of the molecular weights, and dividing the sum by n, and the weight average molecular weight (Mw) indicates the molecular weight distribution of a polymer composition. The molecular weight averages may be expressed in grams per mole (g / mol). The weight average molecular weight and the number average molecular weight may each mean a polystyrene-equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0115] 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 as well as the molecular weight distribution, when the conjugated diene polymer is applied to a rubber composition, the rubber composition has excellent tensile properties, viscoelasticity, and processability, and has an excellent balance of these physical properties.

[0116] According to one embodiment of the present invention, the conjugated diene-based polymer may have a cis-1,4 bond content of 97.0 wt% or more, 97.5 wt% or more, 97.6 wt% or more, 97.9 wt% or more, 98.0 wt% or more, or 98.2 wt% or more, or may be 100.0 wt% or less, 99.5 wt% or less, or 99.0 wt% or less.

[0117] According to one embodiment of the present invention, the conjugated diene-based polymer may have a Mooney viscosity (ML1+4, @100°C) of 30 or more, 35 or more, 40 or more, 42 or more, or 43 or more, and may be 70 or less, 60 or less, 50 or less, 48 ​​or less, or 45 or less.

[0118] Rubber composition The present invention provides a rubber composition. According to an embodiment of the present invention, the rubber composition may contain the conjugated diene polymer. As a specific example, the rubber composition may contain the conjugated diene polymer in an amount of 0.1% by weight or more, 10% by weight or more, or 20% by weight or more, and may contain the conjugated diene polymer in an amount of 100% by weight or less, 95% by weight or less, or 90% by weight or less. Within this range, the wear resistance and crack resistance of a molded product, such as a tire, manufactured using the rubber composition can be sufficiently ensured.

[0119] According to an embodiment of the present invention, the rubber composition may further include other rubber components, if necessary, 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 based on the total weight of the rubber composition. Specifically, the rubber components may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the conjugated diene copolymer.

[0120] 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 (NR) containing cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and 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, polyisobutylene-co-isobutylene copolymer (PCI), polyisobutylene-co-isobutylene copolymer (PCO ... The rubber may be synthetic rubber such as polypropylene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more of these may be used.

[0121] According to an embodiment of the present invention, the rubber composition may include 20 parts by weight or more and 90 parts by weight or less of a filler based on 100 parts by weight of the conjugated diene-based polymer. The filler may be a silica-based filler, a carbon black-based filler, or a combination thereof. As a specific example, the filler may be a carbon black-based filler.

[0122] According to one embodiment of the present invention, the carbon black filler has a nitrogen adsorption specific surface area (NSA, measured in accordance with JIS K 6217-2:2001) of 20 m 2 / g~250m 2 / g. When it is within this range, the rubber composition has excellent processability and the reinforcing performance of the filler can be sufficiently ensured. The carbon black filler may have a dibutyl phthalate oil absorption (DBP) of 80cc / 100g to 200cc / 100g. When it is within this range, the rubber composition has excellent processability and the reinforcing performance of the filler can be sufficiently ensured.

[0123] According to one embodiment of the present invention, the silica-based filler may be wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, colloidal silica, or the like. As a specific example, the silica-based filler may be wet silica, which is most effective in improving fracture properties and wet grip. In addition, the silica-based filler may be a filler having a nitrogen surface area per gram (N2SA) of 120 m 2 / g~180m 2 / g, and the CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area is 100m 2 / g~200m 2 When the molecular weight is within this range, the processability of the rubber composition is excellent and the reinforcing performance of the filler can be sufficiently ensured.

[0124] According to an embodiment of the present invention, when a silica-based filler is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation properties. The 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-triethoxy ... -dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethyl silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, or dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide. As a specific example, in consideration of the effect of improving reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazyl tetrasulfide.

[0125] According to one embodiment of the present invention, the rubber composition may be sulfur crosslinkable, and therefore may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component. When the content is within this range, the vulcanized rubber composition can ensure the required elastic modulus and strength, as well as fuel economy.

[0126] According to an embodiment of the present invention, the rubber composition may further include various additives commonly used in the rubber industry, in addition to the above-mentioned components, specifically, a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

[0127] According to an embodiment of the present invention, the vulcanization accelerator is not particularly limited, but specifically, thiazole compounds such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), or guanidine compounds such as DPG (diphenyl guanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

[0128] According to one embodiment of the present invention, the process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. More specifically, aromatic process oils can be used in consideration of tensile strength and abrasion resistance, and naphthenic or paraffinic process oils can be used in consideration of hysteresis loss and low temperature properties. The process oil may be contained in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component. Within this range, it is possible to prevent a decrease in the tensile strength and low heat generation property (fuel economy) of the vulcanized rubber.

[0129] According to an 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, etc. The antioxidant may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0130] According to one embodiment of the present invention, the rubber composition is obtained by kneading the above-mentioned compounding recipe using a kneading machine such as a Banbury mixer, a roll, or an internal mixer, and after molding, a vulcanization process is performed to obtain a rubber composition having low heat build-up and excellent abrasion resistance.

[0131] According to one embodiment of the present invention, the rubber composition is useful in the manufacture of tire components such as tire treads, undertreads, sidewalls, carcass coating rubbers, belt coating rubbers, bead fillers, chafers, or bead coating rubbers, as well as various industrial rubber products such as dustproof rubbers, belt conveyors, hoses, etc. As a specific example, a molded product manufactured using the rubber composition may include a tire or a tire tread.

[0132] The present invention may be embodied in various different forms and should not be construed as being limited to the embodiments set forth herein.

[0133] Examples and Comparative Examples Example 1 2.1g of 1,3-butadiene diluted to 4.5% by weight in n-hexane was added to the reactor, and 0.6g of neodymium versatate (Solvay) diluted to 40% by weight in n-hexane was added. Then, triethylaluminum was added to the reactor at a temperature of 0°C in an amount of 10 moles of triethylaluminum per mole of neodymium, and stirred for 10 minutes. Then, diisobutylaluminum hydride was added to the reactor at a temperature of 0°C in an amount of 15 moles of diisobutylaluminum hydride per mole of neodymium, and stirred for 30 minutes. Then, diethylaluminum chloride was added to the reactor at a temperature of -5°C in an amount of 3 moles of diethylaluminum chloride per mole of neodymium, and stirred for 30 minutes to prepare a catalyst composition.

[0134] Example 2 2.1 g of 1,3-butadiene diluted to 4.5 wt% in n-hexane was added to the reactor, and 0.6 g of neodymium versatate (Solvay) diluted to 40 wt% in n-hexane was added. Then, triethylaluminum was added to the reactor at a temperature of 0°C in an amount of 10 moles of triethylaluminum per mole of neodymium, and stirred for 10 minutes. Then, triisobutylaluminum was added to the reactor at a temperature of 0°C in an amount of 30 moles of triisobutylaluminum per mole of neodymium, and stirred for 30 minutes. Then, diethylaluminum chloride was added to the reactor at a temperature of -5°C in an amount of 3 moles of diethylaluminum chloride per mole of neodymium, and stirred for 30 minutes to prepare a catalyst composition.

[0135] Example 3 2.1g of 1,3-butadiene diluted to 4.5% by weight in n-hexane was added to the reactor, and 0.6g of neodymium versatate (Solvay) diluted to 40% by weight in n-hexane was added to the reactor. Then, triethylaluminum was added to the reactor at a temperature of 0°C in an amount of 20 moles of triethylaluminum per mole of neodymium, and stirred for 10 minutes. Then, diisobutylaluminum hydride was added to the reactor at a temperature of 0°C in an amount of 15 moles of diisobutylaluminum hydride per mole of neodymium, and stirred for 30 minutes. Then, diethylaluminum chloride was added to the reactor at a temperature of -5°C in an amount of 3 moles of diethylaluminum chloride per mole of neodymium, and stirred for 30 minutes to prepare a catalyst composition.

[0136] Example 4 2.1g of 1,3-butadiene diluted to 4.5% by weight in n-hexane was added to the reactor, and 0.6g of neodymium versatate (Solvay) diluted to 40% by weight in n-hexane was added to the reactor. Then, triethylaluminum was added to the reactor at a temperature of 0°C in an amount of 10 moles of triethylaluminum per mole of neodymium, and stirred for 10 minutes. Then, diisobutylaluminum hydride was added to the reactor at a temperature of 0°C in an amount of 15 moles of diisobutylaluminum hydride per mole of neodymium, and stirred for 30 minutes. Then, ethylaluminum sesquichloride was added to the reactor at a temperature of -5°C in an amount of 2 moles of ethylaluminum sesquichloride per mole of neodymium, and stirred for 30 minutes to prepare a catalyst composition.

[0137] Comparative Example 1 2.1g of 1,3-butadiene diluted to 4.5% by weight in n-hexane was added to the reactor, and 0.6g of neodymium versatate (Solvay) diluted to 40% by weight in n-hexane was added to the reactor. Then, diisobutylaluminum hydride was added to the reactor at a temperature of 0°C in an amount of 15 moles of diisobutylaluminum hydride per mole of neodymium, and stirred for 30 minutes. Then, diethylaluminum chloride was added to the reactor at a temperature of 0°C in an amount of 3 moles of diethylaluminum chloride per mole of neodymium, and stirred for 30 minutes to prepare a catalyst composition.

[0138] Comparative Example 2 2.1 g of 1,3-butadiene diluted to 4.5 wt% in n-hexane and 0.6 g of neodymium versatate (Solvay) diluted to 40 wt% in n-hexane were added to the reactor. Then, triisobutylaluminum was added to the reactor at a temperature of 0°C in an amount of 30 moles of triisobutylaluminum per mole of neodymium and stirred for 30 minutes. Then, diethylaluminum chloride was added to the reactor at a temperature of -5°C in an amount of 3 moles of diethylaluminum chloride per mole of neodymium and stirred for 30 minutes to prepare a catalyst composition.

[0139] Comparative Example 3 2.1g of 1,3-butadiene diluted to 4.5% by weight in n-hexane was added to the reactor, and 0.6g of neodymium versatate (Solvay) diluted to 40% by weight in n-hexane was added. Then, triethylaluminum and diisobutylaluminum hydride were added to the reactor at a temperature of 0°C in amounts of 10 moles of triethylaluminum and 15 moles of diisobutylaluminum hydride per mole of neodymium, respectively, and stirred for 30 minutes. Then, diethylaluminum chloride was added to the reactor at a temperature of 0°C in amounts of 3 moles of diethylaluminum chloride per mole of neodymium, and stirred for 30 minutes to prepare a catalyst composition.

[0140] Experimental Example Experimental Example 1: Production of conjugated diene polymer and evaluation of catalyst composition activity 500g of 1,3-butadiene and 4.2kg of n-hexane were placed in a 20L autoclave reactor, and the internal temperature of the reactor was raised to 70°C. When the catalyst compositions prepared in Examples 1 to 4 were used, 0.01g of diisobutylaluminum hydride was added as a molecular weight modifier to the reactor, and when the catalyst compositions prepared in Comparative Examples 1 to 3 were used, 0.25g of diisobutylaluminum hydride was added as a molecular weight modifier to the reactor, and the catalyst compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were added, and polymerization was performed. When the polymerization conversion rate reached 98% or more, an n-hexane solution containing 1.0g of a polymerization terminator and a solution in which an antioxidant Irganox1520 (BASF) was dissolved in n-hexane at 30% by weight were added to terminate the reaction, and the obtained polymer was put in hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby producing a butadiene polymer.

[0141] During the preparation of the butadiene polymer, a portion of the polymerization solution was taken after 25 minutes of reaction time had elapsed since the start of polymerization to measure the TSC (total solid contents, %), and the polymerization conversion was calculated according to the following mathematical formula 1. The polymerization conversion after 25 minutes of reaction time was measured for each catalyst composition of Examples 1 to 4 and Comparative Examples 1 to 3 to evaluate the activity of the catalyst composition, which is shown in Table 1 below. The measured value of Comparative Example 1 was used as a reference value, and the activity of the catalyst composition of each Example and Comparative Example was indexed according to the following mathematical formula 2.

[0142] The properties of the catalyst compositions produced in Examples 1 to 4 and Comparative Examples 1 to 3 were visually evaluated, and the morphology is shown in Table 1 below.

[0143] [Mathematical formula 1] Polymerization conversion rate (%) = TSC of sample (%) / concentration of 1,3-butadiene added (wt%)

[0144] [Mathematical formula 2] Activity Index = (measured value / reference value) x 100

[0145] [Table 1]

[0146] As shown in Table 1, the catalyst compositions prepared in Examples 1 to 4 exhibited a transparent liquid state as the catalyst solution, confirming that the catalyst compositions were prepared, and showed a significantly higher activity than the catalyst compositions prepared in Comparative Examples 1 to 3.

[0147] In contrast, in Comparative Example 1, in which the pretreatment step using triethylaluminum was not performed on the lanthanum rare earth element compound as in the present invention, it was confirmed that the activity of the catalyst composition was reduced compared to Example 1, in which the same alkylating agent and halide were used.

[0148] In addition, it was confirmed that in Comparative Example 2, in which the pretreatment step using triethylaluminum was not performed on the lanthanum rare earth element compound as in the present invention, the activity of the catalyst composition was reduced compared to Example 2, in which the same alkylating agent and halide were used.

[0149] In addition, in Comparative Example 3 in which a pretreatment step using triethylaluminum was not carried out on the lanthanum rare earth element compound as in the present invention, and triethylaluminum was used as the alkylating agent, a catalyst composition was produced, but it was confirmed that the activity of the catalyst composition was not sufficiently improved compared to Examples 1 to 4.

[0150] Experimental Example 2: Evaluation of physical properties of conjugated diene polymers The conjugated diene polymers prepared in Experimental Example 1 using the catalyst compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were measured for Mooney viscosity, molecular weight distribution, and cis-1,4 bond content as described below, and the results are shown in Table 2 below.

[0151] *Mooney viscosity (ML1+4, @100℃): For each polymer, Mooney viscosity was measured using a Monsanto MV2000E Large Rotor at 100℃ and rotor speed 2±0.02rpm. The sample used was left at room temperature (23±3℃) for 30 minutes or more, and then 27±3g was taken and filled into the die cavity. The platen was operated to apply torque and the Mooney viscosity was measured.

[0152] *Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (MWD): Each polymer was dissolved in tetrahydrofuran (THF) for 30 minutes at 40°C, and then loaded onto gel permeation chromatography (GPC). Two PLgel Olexis columns and one PLgel mixed-C column (Polymer Laboratories) were used as columns. All the newly replaced columns were mixed bed type columns, and polystyrene was used as the standard material for gel permeation chromatography (GPC Standard material).

[0153] *Cis-1,4 bond content: The cis-1,4 bond content of the conjugated diene portion was measured by Fourier transform infrared spectroscopy (FT-IR). Specifically, carbon disulfide in the same cell was used as a blank, and the FT-IR transmittance spectrum of a carbon disulfide solution of a conjugated diene polymer prepared at a concentration of 5 mg / mL was measured. -1 The maximum peak value (a, baseline) near 967 cm represents the trans-1,4 bond. -1 The minimum peak value (b) near 911 cm represents a vinyl bond. -1 The minimum peak value (c) near 736 cm, which represents the cis-1,4 bond -1 The respective contents were calculated using the minimum peak value (d) in the vicinity.

[0154] [Table 2]

[0155] As shown in Table 2, it was confirmed that the conjugated diene-based polymers produced using the catalyst compositions produced in Examples 1 to 4 exhibited appropriate levels of Mooney viscosity and molecular weight distribution, and also ensured a high level of cis-1,4 bond content. In particular, it was confirmed that the conjugated diene-based polymers produced using the catalyst compositions produced in Examples 1, 2 and 4 were excellent in Mooney viscosity, molecular weight distribution and cis-1,4 bond content.

[0156] In contrast, the conjugated diene polymers produced using the catalyst compositions produced in Comparative Examples 1 to 3 had broad molecular weight distributions and a lower cis-1,4 bond content than those in Examples 1, 2, and 4. In particular, it was confirmed that the conjugated diene polymer produced using the catalyst composition produced in Comparative Example 3 not only had a lower cis-1,4 bond content than those in Examples 1 to 4, but also had a broad molecular weight distribution and a very low level of Mooney viscosity.

[0157] Experimental Example 3: Evaluation of physical properties of rubber composition Using the conjugated diene-based polymers produced in Experimental Example 1 using the catalyst compositions of Examples 1 to 4 and Comparative Examples 1 to 3, rubber compositions and rubber test pieces were produced, and the Mooney viscosity, abrasion resistance, tensile properties, and viscoelastic properties of the rubber compositions were measured by the following methods, and the results are shown in Table 3 below.

[0158] <Production of Rubber Composition and Rubber Test Pieces> The conjugated diene polymers produced in Experimental Example 1 using the catalyst compositions of Examples 1 to 4 and Comparative Examples 1 to 3 were mixed with 70 parts by weight of carbon black, 22.5 parts by weight of process oil (TDAE oil), 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO), and 2 parts by weight of stearic acid to produce the conjugated diene polymers.

[0159] Then, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), and 0.5 parts by weight of vulcanization accelerator (DPG) were added to each of the rubber compositions, and the mixture was weakly mixed at 50 rpm for 1 minute 30 seconds at 50°C. A sheet-shaped vulcanization mixture was then produced using a roll at 50°C, and the vulcanization mixture was vulcanized at 160°C for 25 minutes to produce rubber test pieces.

[0160] *Tensile properties: After vulcanizing each rubber composition prepared above for 90 minutes at 150°C, the modulus at 300% elongation of the vulcanized product (M-300%, kg f / cm) was measured in accordance with ASTM D412. 2 The measured value of Comparative Example 1 was used as a reference value, and the 300% modulus of each of the Examples and Comparative Examples was indexed according to the following Equation 3.

[0161] [Mathematical formula 3] M-300% Index = (measured value / reference value) x 100

[0162] * Viscoelastic properties: Using a DMTS 500N manufactured by Gabo, Germany, the viscoelastic coefficient (Tan δ) was measured at a frequency of 10 Hz, a prestrain of 3%, and a dynamic strain of 3% at temperatures from -60°C to 60°C. At this time, the Tan δ value at 0°C indicates road resistance, and the Tan δ value at 60°C indicates rolling resistance properties (fuel economy). 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 mathematical formula 4.

[0163] [Mathematical formula 4] Tanδ60℃ Index = (reference value / measured value) × 100

[0164] *Abrasion resistance: A DIN abrasion test was performed on each rubber test piece prepared above according to ASTM D5963, and the results were expressed as DIN wt loss 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 according to the following mathematical formula 5.

[0165] [Mathematical formula 5] Wear Index = (reference value / measured value) x 100

[0166] [Table 3]

[0167] As shown in Table 3, the rubber compositions containing the conjugated diene polymers prepared using the catalyst compositions prepared in Examples 1 to 4 were confirmed to have improved tensile properties, viscoelastic properties, and abrasion resistance compared to the rubber composition containing the conjugated diene polymer prepared using the catalyst composition prepared in Comparative Example 1.

[0168] In contrast, it was confirmed that the rubber composition produced containing the conjugated diene polymer produced using the catalyst composition produced in Comparative Example 2 had inferior tensile properties, viscoelastic properties, and abrasion resistance compared to the rubber composition produced containing the conjugated diene polymer produced using the catalyst composition produced in Comparative Example 1.

[0169] In addition, it was confirmed that the rubber composition produced containing the conjugated diene polymer produced using the catalyst composition produced in Comparative Example 3 showed minimal improvement in tensile properties, viscoelastic properties, and abrasion resistance, and was at the same level as the rubber composition produced containing the conjugated diene polymer produced using the catalyst composition produced in Comparative Example 1.

[0170] This result is attributable to the fact that the catalytic activity was improved by pretreating hydrogen-bonded lanthanum rare earth compounds and / or oligomer forms of lanthanum rare earth compounds, which cause a decrease in catalytic activity, prior to the alkylation reaction during the preparation of the catalyst composition for producing a conjugated diene polymer.

[0171] From these results, it was confirmed that the catalyst composition prepared by the method for preparing a catalyst composition of the present invention has excellent catalytic activity because it is prepared by pretreating hydrogen-bonded lanthanum rare earth compounds and / or oligomer forms of lanthanum rare earth compounds, which cause a decrease in catalytic activity, prior to the alkylation reaction.

[0172] In addition, it has been confirmed that the conjugated diene polymer produced by the method for producing a conjugated diene polymer of the present invention has a low content of lanthanum-based rare earth elements remaining in the conjugated diene polymer due to its high catalytic activity, a high content and linearity of cis bonds, and a narrow molecular weight distribution, and when applied to a rubber composition, it exhibits excellent wear resistance and low fuel consumption.

Claims

1. A pretreatment step (S10) of carrying out a pretreatment reaction on a hydrogen bond, an oligomer form, or a combination thereof of a lanthanum rare earth compound; an alkylation reaction step (S20) of mixing and reacting the lanthanum rare earth compound pretreated in the step (S10) with an alkylating agent; and a halogenation reaction step (S30) of mixing and reacting the lanthanum rare earth compound alkylated in the step (S20) with a halide.

2. 2. The method for producing a catalyst composition according to claim 1, wherein the step (S10) is carried out by mixing and reacting the lanthanum rare earth compound with one or more trialkylaluminums selected from the group consisting of trimethylaluminum and triethylaluminum.

3. The method for producing a catalyst composition according to claim 2, wherein the step (S10) is performed before an alkylation reaction of the lanthanum rare earth compound with trialkylaluminum occurs.

4. The method for producing a catalyst composition according to claim 1, wherein the lanthanum rare earth element compound is a neodymium compound represented by the following chemical formula 1: 【Chemistry 5】 (In the above Chemical Formula 1, R 1 ~R 3 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 1 ~R 3 cannot all be hydrogen.)

5. The lanthanum rare earth element compound is Nd(2-ethylhexanoate). 3 , Nd(2,2-dimethyldecanoate) 3 , Nd(2,2-diethyldecanoate) 3 , Nd(2,2-dipropyl decanoate) 3 , Nd(2,2-dibutyldecanoate) 3 , Nd(2,2-dihexyldecanoate) 3 , Nd(2,2-dioctyldecanoate) 3 , Nd(2-ethyl-2-propyl decanoate) 3 , Nd(2-ethyl-2-butyldecanoate) 3 , Nd(2-ethyl-2-hexyldecanoate) 3 , Nd(2-propyl-2-butyldecanoate) 3 , Nd(2-propyl-2-hexyldecanoate) 3 , Nd(2-propyl-2-isopropyl decanoate) 3 , Nd(2-butyl-2-hexyldecanoate) 3 , Nd(2-hexyl-2-octyldecanoate) 3 , Nd(2,2-diethyl octanoate) 3 , Nd(2,2-dipropyl octanoate) 3 , Nd(2,2-dibutyl octanoate) 3 , Nd(2,2-dihexyl octanoate) 3 , Nd(2-ethyl-2-propyl octanoate) 3 , Nd(2-ethyl-2-hexyl octanoate) 3 , Nd(2,2-diethylnonanoate) 3 , Nd(2,2-dipropyl nonanoate) 3 , Nd(2,2-dibutylnonanoate) 3 , Nd(2,2-dihexylnonanoate) 3 , Nd(2-ethyl-2-propyl nonanoate) 3 , and Nd(2-ethyl-2-hexylnonanoate) 3 The method for producing a catalyst composition according to claim 1, wherein the catalyst is one or more selected from the group consisting of:

6. The method for producing a catalyst composition according to claim 1, wherein the alkylating agent is an alkylaluminum compound represented by the following formula 2: [Chemical formula 2] AlR 4 R 5 R 6 (In the above Chemical Formula 2, R 4 ~R 6 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R 4 ~R 6 Not all of R are hydrogen. 4 ~R 6 When all of are alkyl groups, the alkyl groups have 3 to 12 carbon atoms.

7. 2. The method of claim 1, wherein the alkylating agent is a dialkylaluminum hydride.

8. 2. The method for producing a catalyst composition according to claim 1, wherein the pretreatment reaction in step (S10), the alkylation reaction in step (S20), or the pretreatment reaction in step (S10) and the alkylation reaction in step (S20) are carried out using a conjugated diene monomer.

9. The method for producing a catalyst composition according to claim 1, wherein the halide is at least one selected from the group consisting of alkylaluminum halides represented by the following formula 3 and alkylaluminum sesquihalides represented by the following formula 4. [Chemical formula 3] AlR 7 R 8 R 9 In the above Chemical Formula 3, R 7 ~R 9 are each independently a halogen group or an alkyl group having 1 to 12 carbon atoms, R 7 ~R 9 Not all of the groups are halogen groups, 【Chemistry 6】 In the above Chemical Formula 4, R 10 ~R 12 are each independently an alkyl group having 1 to 12 carbon atoms, X 1 ~X 3 are each independently a halogen group.

10. The method for producing a catalyst composition according to claim 1, wherein the halide is at least one selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides.

11. A method for producing a conjugated diene polymer, comprising: 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 according to claim 1 to produce an activated polymer (S100).

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