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 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] This application claims priority under Korean Patent Application No. 10-2022-0021075 dated 17 February 2022, 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] Recently, with the growing concern for energy conservation and environmental issues, there is a 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 to form tires, while also reducing 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, 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 reducing the molecular weight distribution, lanthanum-based rare earth element compounds are mainly used.

[0006] Typical examples of the aforementioned lanthanum-based rare earth element compounds include neodymium compounds, with specific examples including NdV (neodymium versatate). These are activated by an alkylation reaction using an alkylaluminum compound, followed by a halogenation reaction using an alkylaluminum halide compound. To stabilize the catalyst, preforming may be carried out during the alkylation reaction by adding a 1,3-butadiene monomer.

[0007] Here, the same lanthanum-based rare earth element compounds, such as NdV, do not exist in single-compound form, but rather in a form where they are hydrogen-bonded by water and aliphatic compounds used in the manufacturing process, and / or in oligomeric form (Non-Patent Documents 1 and 2). However, when alkylation is immediately performed on hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomeric forms of lanthanum-based rare earth element compounds, alkylation takes a longer time and is insufficient 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. To overcome the drawbacks of manufacturing catalyst systems in batch mode, Patent Document 1 specifies the type of reactor, adjusts the flow rate at the outlet of the catalyst system at the line outlet as needed, and allows the system to remain within a residual time range suitable for the alkylation and chlorination reactions, in order to prevent gel formation in the reactor and ensure the flexibility of the alkylating agent and rare earth element salts that affect catalytic activity when manufacturing continuously. 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 recognize the form of the lanthanum compound added during the alkylation reaction or its effect on catalytic activity. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] US9056303 B2 [Patent Document 2] JP5072191 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 catalyst compositions for the polymerization of polybutadiene by pretreatment before the alkylation reaction 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, when continuously producing such compositions.

[0012] In other words, the present invention aims to provide a continuous manufacturing 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 mentioned in the background art 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, high linearity, and a narrow molecular weight distribution using a catalyst composition produced by the above-mentioned method for producing a catalyst composition. [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.

[0015] (1) The present invention provides a method for producing a catalyst composition comprising: a pretreatment step (S10) in which a lanthanum-based rare earth element compound is subjected to a pretreatment reaction to form hydrogen bonds, an oligomer, or a combination thereof; an alkylation reaction step (S20) in which the lanthanum-based rare earth element compound, which has been pretreated in step (S10) to form hydrogen bonds, an oligomer, or a combination thereof, is mixed with an alkylating agent and reacted; and a halogenation reaction step (S30) in which the lanthanum-based rare earth element compound, which has been alkylated in step (S20), is mixed with a halogen compound and reacted, wherein steps (S10), (S20), and (S30) are carried out in separate reactors connected in series.

[0016] (2) The present invention provides a method for producing a catalyst composition, wherein step (S10) in (1) 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 trimethylaluminum and triethylaluminum.

[0017] (3) The present invention provides a method for producing a catalyst composition in which, in (2) above, step (S10) is carried out up to the point before the alkylation reaction with trialkylaluminum is performed on the lanthanum-based rare earth element compound.

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

[0019] [ka]

[0020] 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, but R 1 ~R 3 But it's not all hydrogen.

[0021] (5) In any one of the above (1) to (4), the present invention provides a method for producing a catalyst composition, wherein the lanthanum-based rare earth element compound is one or more selected from the group consisting of Nd(2-ethylhexanoate)3, Nd(2,2-dimethyldecanoate)3, Nd(2,2-diethyldecanoate)3, Nd(2,2-dipropyldecanoate)3, Nd(2,2-dibutyldecanoate)3, Nd(2,2-dihexyldecanoate)3, Nd(2,2-dioctyldecanoate)3, Nd(2-ethyl-2-propyldecanoate)3, Nd(2-ethyl-2-butyldecanoate)3, Nd(2-ethyl-2-hexyldecanoate)3, Nd(2-propyl-2-butyldecanoate)3, Nd(2-propyl-2-hexyldecanoate)3, Nd(2-propyl-2-isopropyldecanoate)3, Nd(2-butyl-2-hexyldecanoate)3, Nd(2-hexyl-2-octyldecanoate)3, Nd(2,2-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).

[0022] (6) In any one of the above (1) to (5), the present invention provides a method for producing a catalyst composition, 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 In Chemical Formula 2 above, R 4 ~R 6Each is independently either hydrogen or an alkyl group having 1 to 12 carbon atoms, but R 4 ~R 6 Not all of them are hydrogen, but R 4 ~R 6 If all of the elements are alkyl groups, the number of carbon atoms in each alkyl group is between 3 and 12.

[0024] (7) The present invention provides a method for producing a catalyst composition in which, in any one of (1) to (6) above, the alkylating agent is a dialkylaluminum hydride.

[0025] (8) The present invention provides a method for producing a catalyst composition in which, in any one of (1) to (7) above, 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 with a conjugated diene monomer.

[0026] (9) The present invention provides a method for producing a catalyst composition in any one of (1) to (8) above, wherein the halogen compound 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.

[0027] [Chemical formula 3] AlR 7 R 8 R 9 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, but R 7 ~R 9 Not all of them are halogen groups,

[0028] [ka]

[0029] In the above chemical formula 4, R 10 ~R12 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] (10) The present invention provides a method for producing a catalyst composition in any one of (1) to (9) above, wherein the halogen compound is one or more selected from the group consisting of dialkylaluminum halides and alkylaluminum sesquihalides.

[0031] (11) The present invention provides a method for producing a catalyst composition in which, in any one of (1) to (10) above, steps (S10), (S20), and (S30) are carried out in succession.

[0032] (12) The present invention provides a method for producing a conjugated diene polymer, comprising the step (S100) of polymerizing a conjugated diene monomer in the presence of a catalyst composition produced by a method for producing a catalyst composition using any one of the hydrocarbon solvents described in (1) to (11) above, in order to produce an active polymer.

[0033] (13) The present invention provides a conjugated diene polymer produced by the method for producing a conjugated diene polymer according to (12) above.

[0034] (14) The present invention provides a rubber composition comprising a conjugated diene polymer according to (13) above. [Effects of the Invention]

[0035] The catalyst composition produced by the method for producing the catalyst composition of the present invention has 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, before the alkylation reaction.

[0036] The method for producing catalyst compositions according to the present invention makes it possible to continuously produce catalyst compositions, thereby improving the productivity of catalyst compositions and conjugated diene polymers using them, and ensuring more uniform quality.

[0037] 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 lanthanum-based rare earth elements remaining within the polymer, 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]

[0038] The present invention will be described in more detail below to aid in understanding the present invention.

[0039] 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 in a manner consistent with the technical idea of ​​this invention, in accordance with the principle that inventors may define the concepts of terms as appropriate to best describe their invention.

[0040] 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.

[0041] According to one embodiment of the present invention, the method for producing the catalyst composition includes a pretreatment step (S10) in which a pretreatment reaction is carried out to a lanthanum-based rare earth element compound to form hydrogen bonds, an oligomer, or a combination thereof; an alkylation reaction step (S20) in which the lanthanum-based rare earth element compound, which has been pretreated in step (S10) to form hydrogen bonds, an oligomer, or a combination thereof, is mixed with an alkylating agent and reacted; and a halogenation reaction step (S30) in which the lanthanum-based rare earth element compound, which has been alkylated in step (S20), is mixed with a halogen compound and reacted. Steps (S10), (S20), and (S30) can each be carried out in separate reactors connected in series.

[0042] As described in the background art of the present invention, lanthanum-based rare earth element compounds do not exist in single compound form, but rather in a form where they are hydrogen-bonded by water and aliphatic compounds used in the manufacturing process, and / or in oligomeric form (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 oligomeric forms of lanthanum-based rare earth element compounds, the alkylation takes a longer time and the alkylation reaction is not carried out 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 carrying out a halogenation reaction, it can cause a decrease in catalytic activity and increase contamination of the catalyst manufacturing equipment. However, the method for producing a 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 oligomeric form of the lanthanum-based rare earth element compound in step (S10) before the alkylation reaction. Here, the pretreatment may include minimizing, or even removing, hydrogen-bonded lanthanum-based rare earth element compounds and / or oligomeric forms of lanthanum-based rare earth element compounds before the alkylation reaction.

[0043] According to one embodiment of the present invention, step (S10) can be carried out by mixing a lanthanum-based rare earth element compound with one or more trialkylaluminum selected from the group consisting of trimethylaluminum and triethylaluminum and reacting them. Trimethylaluminum and triethylaluminum are known to be usable as alkylating agents in alkylation reactions. However, if trimethylaluminum and triethylaluminum are used simply as alkylating agents, rather than to carry out the pretreatment reaction in step (S10) as in the present invention, then depending on the purpose, the alkylation reaction with the lanthanum-based rare earth element compound can be induced, which means that the alkylation reaction takes a long time and causes the problem of the alkylation reaction not being carried out sufficiently. From this viewpoint, step (S10) can be carried out up to the point before the alkylation reaction with one or more trialkylaluminum selected from the group consisting of trimethylaluminum and triethylaluminum is carried out with the lanthanum-based rare earth element compound. On the other hand, trialkylaluminum and / or dialkylaluminum hydrides that can be used as alkylating agents other than trimethylaluminum and triethylaluminum cannot adequately induce hydrogen bonding, oligomeric forms, or combinations thereof in pretreatment reactions with lanthanum-based rare earth element compounds, and are therefore not suitable as trialkylaluminum compounds for the pretreatment reaction in step (S10).

[0044] According to one embodiment of the present invention, step (S10) can be carried out by adding one or more trialkylaluminum selected from the group consisting of trimethylaluminum and triethylaluminum 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.

[0045] According to one embodiment of the present invention, step (S10) can be carried out at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, and can also be carried out 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, step (S10) can be carried out for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more, and can also be carried out 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, step (S10) can be performed to 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 between the lanthanum-based rare earth element compound and one or more trialkylaluminum selected from the group consisting of trimethylaluminum and triethylaluminum, the reaction temperature, and the reaction time.

[0048] According to one embodiment of the present invention, the lanthanum-based rare earth element compound may be a neodymium compound, and specific examples 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.); organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium dihexyl phosphate, etc.). Neodymium phosphates, 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.); carbamates (e.g., neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate) Salts, such as neodymium dibutylcarbamate or neodymium dibenzylcarbamate); dithiocarbamates (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate or neodymium dibutyldithiocarbamate); xanthogenic salts (e.g., neodymium methylxanthogenic salt, neodymium ethylxanthogenic salt, neodymium isopropylxanthogenic salt, neodymium butylxanthogenic salt, or neodymium benzylxanthogenic salt);β-diketonates (e.g., neodymium acetylacetonate, neodymium triple oloacetylacetonate, 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 fluoride, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium iodide); Examples include ozym 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 mixtures of any one or more of these may be included.

[0049] 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.

[0050] [ka]

[0051] 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, but R 1 ~R 3 It is not necessary for all of them to be hydrogen. For example, 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, but R 2and R 3 It is not necessary for all of them to be hydrogen. As a more specific example, 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, but R 2 and R 3 It doesn't have to be all hydrogen.

[0052] 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 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-Hexyldecanoate)3 It may be one or more selected from the group consisting of xyloctanoate)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.

[0053] 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 a steric change 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.

[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 a nonpolar solvent at room temperature (25°C). The solubility of the neodymium compound refers to the degree to which it dissolves cleanly without suspension phenomena, and by exhibiting such high solubility, it is possible to show excellent catalytic activity.

[0055] According to one embodiment of the present invention, step (S10) can be carried out including a conjugated diene monomer. This is for pre-mixing a conjugated diene monomer, which will be used in the polymerization reaction of a conjugated diene polymer using the catalyst composition produced by the present invention, with the catalyst composition to form a pre-polymerized or pre-mixed catalyst composition, thereby further improving the activity of the catalyst composition and stabilizing the active polymer produced. "Pre-polymerization" may mean adding a small amount of a conjugated diene monomer, such as 1,3-butadiene, to the catalyst composition containing a neodymium compound, an alkylating agent, and a halogen compound, i.e., to reduce the possibility of generating active species of various catalyst compositions in the catalyst system, and that pre-polymerization takes place in the catalyst composition system along with the addition of 1,3-butadiene. "Pre-mixing" may mean a state in which polymerization does not take place 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 introduced 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 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.

[0057] According to one embodiment of the present invention, when step (S10) is carried out including a conjugated diene monomer, the conjugated diene monomer can 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 it can 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 carrying out an alkylation reaction of a lanthanum-based rare earth element compound, which can be carried out by mixing and reacting an alkylating agent with a lanthanum-based rare earth element compound that has been pretreated in step (S10) to have hydrogen bonds, oligomer form, or a combination thereof.

[0059] 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.

[0060] According to one embodiment of the present invention, the alkylating agent may be an organoaluminum compound, and specific examples 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. Dihydrocarbyl aluminum hydrides such as hydrides, 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.

[0061] 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 the lanthanum-based rare earth compound pretreated in step (S10) in the form of hydrogen bonds, oligomers, or a combination thereof. As a specific example, the alkylating agent may be an alkylaluminum compound represented by the following chemical formula 2.

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

[0063] 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, but R 4 ~R 6 Not all of them are hydrogen, but R 4 ~R 6 If all of them are alkyl groups, the number of carbon atoms in the alkyl group may be 3 to 12. As a specific example, 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, but R 4 ~R 6 Not all of them are hydrogen, but R 4 ~R 6 If all of them 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 Each is independently either hydrogen or an alkyl group having 3 to 6 carbon atoms, but R 4 ~R 6 It doesn't have to be all hydrogen.

[0064] 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 the lanthanum-based rare earth element compound pretreated in step (S10) in the form of hydrogen bonds, oligomers, 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. Specifically, the alkylating agent may include two or more selected from the group consisting of dialkylaluminum hydrides and trialkylaluminum. More specifically, the alkylating agent may include one or more dialkylaluminum hydrides and one or more trialkylaluminums, and more specifically, the alkylating agent may include diisobutylaluminum hydride and triisobutylaluminum.

[0066] According to one embodiment of the present invention, step (S20) can 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 to 1 mole of a lanthanum-based rare earth element compound that has been pretreated in step (S10) to form hydrogen bonds, oligomers or a combination thereof. Alternatively, it can be carried out by adding an alkylating agent in a molar ratio of 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.

[0067] According to one embodiment of the present invention, step (S20) can be carried out at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, and can also be carried out 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, step (S20) can be carried out for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more, and can also be carried out 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.

[0069] According to one embodiment of the present invention, step (S20) can be further enhanced by adjusting the molar ratio of the lanthanum-based rare earth element compound, which has been pretreated in step (S10) to form an oligomer, or a combination thereof, to the alkylating agent, the reaction temperature, and the reaction time.

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

[0071] According to one embodiment of the present invention, when step (S20) is carried out including a conjugated diene monomer, the conjugated diene monomer can 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 step (S10) to form hydrogen bonds, oligomers, or a combination thereof, or it can 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.

[0072] According to one embodiment of the present invention, step (S30) is a step for carrying out a halogenation reaction with the lanthanum-based rare earth element compound alkylated in step (S20), and can be carried out by mixing the lanthanum-based rare earth element compound alkylated in step (S20) with a halogen compound and reacting them.

[0073] According to one embodiment of the present invention, the halogen compound may be an elemental halogen, an interhalogen compound, a hydrogen halide, an organic halide, a nonmetallic halide, a metal halide, or an organometallic halide.

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

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

[0076] According to one embodiment of the present invention, the hydrogen halogen 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-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 ("iodomethane"). 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.

[0078] 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.

[0079] 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.

[0080] According to one embodiment of the present invention, the organometallic halide may be an alkylaluminum halide or an alkylaluminum sesquihalide.As a specific example, the organometallic halides 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-butyltin 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 These may include nium 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 halogen compound 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.

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

[0083] 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, but R 7 ~R 9 Not all of them are halogen groups. For example, 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, but R 7 ~R 9 Not all of them are halogen groups. As a more specific example, 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.

[0084] [ka]

[0085] 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. As a specific example, 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. As a more specific example, in the above chemical formula 4, R 10 ~R 12Each of these may independently be an alkyl group having 1 to 4 carbon atoms.

[0086] According to one embodiment of the present invention, the halogen compound 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 reaction by the lanthanum-based rare earth element compound pretreated in step (S10) to 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 one embodiment of the present invention, step (S30) can be carried out by adding a halogen compound 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 to 1 mole of a lanthanum-based rare earth element compound that has been pretreated in step (S10) to form hydrogen bonds, oligomers, or a combination thereof, or by adding a halogen compound 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.

[0088] According to one embodiment of the present invention, step (S30) can be carried out at a temperature of -20°C or higher, -15°C or higher, or -10°C or higher, and can also be carried out 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, step (S30) can be carried out for 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, or 30 minutes or more, and can also be carried out 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, step (S30) can further improve catalytic activity by adjusting the molar ratio of the lanthanum-based rare earth compound and the halogen compound, the reaction temperature and reaction time, which have been pretreated in step (S10) to obtain hydrogen bonds, oligomer form, or a combination thereof.

[0091] According to one embodiment of the present invention, steps (S10) to (S30) can 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. Specific examples of the organic solvent may be linear, branched, or cyclic aliphatic hydrocarbons 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 or 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 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.

[0092] According to one embodiment of the present invention, steps (S10), (S20), and (S30) can each be carried out in separate reactors connected in series. Therefore, three reactors are required to produce a catalyst by the method for producing the catalyst composition.

[0093] According to one embodiment of the present invention, steps (S10), (S20), and (S30) can be carried out in succession. That is, steps (S10), (S20), and (S30) can be carried out in succession in separate reactors connected in series, in which 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, the flow of reactants in individual reactors connected in series can be carried out independently in a top-down or bottom-up manner.

[0095] According to one embodiment of the present invention, all steps of the method for producing the catalyst composition, including steps (S10) to (S30), can be carried out at a temperature of -20°C or higher, -15°C or higher, -10°C or higher, or -5°C or higher, and can also be carried out 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.

[0096] According to one embodiment of the present invention, all steps of the method for producing the catalyst composition, including steps (S10) to (S30), can be carried out for 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, 55 minutes or more, 60 minutes or more, 65 minutes or more, or 70 minutes or more, and can also be carried out 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.

[0097] Method for producing conjugated diene polymers This invention provides a method for producing conjugated diene polymers.

[0098] 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 can 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 total conjugated diene monomers, 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 less.

[0102] According to one embodiment of the present invention, the polymerization in step (S100) can be carried out by continuous polymerization in a polymerization reactor including at least two reactors, or by 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 autoreaction heat without adding any heat after the catalyst composition is added, temperature-increasing polymerization means increasing the temperature by adding heat after the catalyst composition is added, and isothermal polymerization means either increasing the heat by adding heat after the catalyst composition is added, or maintaining a constant temperature of the reactants by removing heat.

[0104] According to one embodiment of the present invention, the polymerization in step (S100) can be carried out using coordination anionic polymerization, and the polymerization environment may be bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and a specific example may be solution polymerization.

[0105] According to one embodiment of the present invention, the polymerization in step (S100) can be carried out at a temperature of -20°C or higher, -10°C or higher, 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, or 60°C or higher, and can also be carried out at a temperature of 200°C or lower, 150°C or lower, 120°C or lower, or 90°C or lower. 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) can be carried out for 15 minutes or more, 20 minutes or more, 30 minutes or more, 40 minutes or more, 50 minutes or more, or 1 hour or more, and can also be carried out 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] One embodiment of the present invention 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, after producing the active polymer, a step of further terminating the polymerization 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. In addition, additives that facilitate solution polymerization, such as chelating agents, dispersants, pH adjusters, oxygen scavengers, etc., may be selectively used in conjunction with the reaction termination agent.

[0110] Conjugated diene polymers This invention provides conjugated diene polymers.

[0111] According to one embodiment of the present invention, the conjugated diene polymer can be produced by the method for producing the conjugated diene polymer. That is, the conjugated diene polymer can be polymerized in the presence of a catalyst composition produced by the method for producing the catalyst composition described above.

[0112] 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.

[0113] 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 optionally contain 20% or less, 15% or less, 10% or less, or 5% or less by weight of other conjugated diene monomer units copolymerizable with 1,3-butadiene monomers, 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 include 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.

[0114] 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.

[0115] According to one embodiment of the present invention, the conjugated diene polymer has a weight-average molecular weight (Mw) of 1.0 × 10⁻⁶ 5 g / mol or more, 2.0×10 5 g / mol or more, 3.0×10 5 g / mol or more, 4.0×10 5 g / mol or more, 5.0×10 5 g / mol or more, 6.0×10 5 g / mol or more, 7.0×10 5 g / mol or more, 8.0×10 5 g / mol or more or 9.0 × 10⁻⁶ 5 It may be greater than or equal to g / mol, and also 1.0 × 10 6 g / mol or less, 9.0×10 5less than g / mol, 8.0×10 5 less than g / mol, 7.0×10 5 less than g / mol, 6.0×10 5 less than g / mol, 5.0×10 5 less than g / mol, 4.0×10 5 less than g / mol, or 3.0×10 5 less than g / mol may also be acceptable. Further, the conjugated diene polymer has a number average molecular weight (Mn) of 1.0×10 5 g / mol or more, 2.0×10 5 g / mol or more, 3.0×10 5 g / mol or more, 4.0×10 5 g / mol or more, or 5.0×10 5 g / mol or more may also be acceptable, and 6.0×10 5 g / mol or less, 5.0×10 5 g / mol or less, 4.0×10 5 g / mol or less, 3.0×10 5 g / mol or less, 2.0×10 5 g / mol or less, or 1.0×10 5 g / mol or less may also be acceptable. Within this range, when applied to the rubber composition, it has excellent tensile properties and excellent processability, so kneading is easy due to the improvement of the workability of the rubber composition, and it has the effect of excellent mechanical properties and property balance of the rubber composition.

[0116] 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). Here, 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, determining the sum of 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 represent the polystyrene-equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0117] 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 simultaneously with the molecular weight distribution, when applied to a rubber composition, it exhibits excellent tensile properties, viscoelasticity, and processability for the rubber composition, and has the effect of having an excellent balance of these physical properties.

[0118] According to one embodiment of the present invention, the conjugated diene polymer may have a cis-1,4 bond content of 97.0% by weight or more, 97.5% by weight or more, 97.6% by weight or more, 97.9% by weight or more, 98.0% by weight or more, or 98.1% by weight or more, and may also have a content of 100.0% by weight or less, 99.5% by weight or less, or 99.0% by weight or less.

[0119] According to one embodiment of the present invention, the conjugated diene polymer may have a Mooney viscosity (ML1+4, @100℃) of 30 or more, 35 or more, 40 or more, 42 or more, or 45 or more, and may also have a viscosity of 70 or less, 60 or less, 50 or less, 48 ​​or less, or 47 or less.

[0120] rubber composition This invention provides a rubber composition.

[0121] 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 100% or less by weight, 95% or less by weight, or 90% or less by weight, and within this range, sufficient wear resistance and crack resistance can be ensured for molded articles manufactured using the rubber composition, such as tires.

[0122] 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. Here, 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.

[0123] 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 copolymer. Synthetic rubbers such as soprene, 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, and halogenated butyl rubber may be used, and one or more of these mixtures may be used.

[0124] 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. As a specific example, the filler may be a carbon black-based filler.

[0125] 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 K 6217-2:2001) of 20 m². 2 / g~250m 2 The amount may be as low as / g, and within this range, the processability of the rubber composition can be 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, and within this range, the processability of the rubber composition can be excellent, and sufficient reinforcement performance by the filler can be ensured.

[0126] 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. As a specific example, 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 The value may be as low as / g, and within this range, the rubber composition can be made to have excellent processability and sufficient reinforcement performance due to the filler.

[0127] According to one embodiment of the present invention, when a silica-based filler is used as the filler, a silane coupling agent can be used together 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 -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 may also be used. Specifically, the silane coupling agent may be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, considering the effect of improving reinforcing properties.

[0128] According to one embodiment of the present invention, the rubber composition may be sulfur crosslinkable, thereby further containing 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, the necessary elastic modulus and strength of the vulcanized rubber composition can be ensured, as well as low fuel consumption.

[0129] According to one embodiment of the present invention, the rubber composition may further contain, in addition to the above-mentioned 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.

[0130] According to one embodiment of the present invention, the vulcanization accelerator is not particularly limited, and specifically, thiazole compounds such as M (2-mercaptobenzothiazole), DM (dibenzothiadyl disulfide), CZ (N-cyclohexyl-2-benzothiadylsulfenamide), or guanidine compounds such as DPG (diphenylguanidine) can be used. 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.

[0131] According to one embodiment of the present invention, the process oil acts as a softening agent in the rubber composition and may be, as a specific example, 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, and within this range, a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber can be prevented.

[0132] According to one embodiment of the present invention, the anti-aging agent may be N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone. The anti-aging agent can be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of the rubber component.

[0133] 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 according to the formulation, and after molding, a rubber composition with low heat generation and excellent abrasion resistance can be obtained by a vulcanization process.

[0134] According to one embodiment of the present invention, the rubber composition can be used in the manufacture of various tire components such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, shapers, or bead coating rubber, as well as various industrial rubber products such as vibration damping rubber, belt conveyors, and hoses. As a specific example, a molded product manufactured using the rubber composition may include a tire or a tire tread.

[0135] Hereinafter, embodiments of the present invention will be described in detail 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 can be realized in various different forms and is not limited to the embodiments described herein.

[0136] Examples <Example 1> Three pressure-resistant reactors, each with a volume of 300 ml and equipped with jackets and stirrers, were connected in series and used as a continuous catalyst production reactor. A nitrogen atmosphere was maintained in each reactor. A neodymium versatate solution diluted in n-hexane was continuously injected into the first reactor, simultaneously with 1,3-butadiene diluted in n-hexane, and a triethylaluminum solution diluted in n-hexane was continuously injected at a concentration of 10 moles of triethylaluminum per mole of neodymium. The first reactor was operated at a temperature of 0°C, and after 10 minutes of continuous injection, the mixture from the first reactor was transferred to the second reactor, into which a diisobutylaluminum hydride solution diluted in n-hexane was continuously injected at a concentration of 15 moles of diisobutylaluminum hydride per mole of neodymium. The second reactor was operated at a temperature of 0°C. After 30 minutes of continuous injection, the reactants from the second reactor were transferred to the third reactor, into which a diethylaluminum chloride solution diluted with n-hexane was continuously injected at a concentration of 3 moles of diethylaluminum chloride per 1 mole of neodymium. The third reactor was operated at a temperature of -5°C. After 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature below 0°C.

[0137] <Example 2> Three pressure-resistant reactors, each with a volume of 300 ml and equipped with jackets and stirrers, were connected in series and used as a continuous catalyst production reactor. A nitrogen atmosphere was maintained in each reactor. A neodymium versatate solution diluted in n-hexane was continuously injected into the first reactor, simultaneously with a 1,3-butadiene solution diluted in n-hexane, and a triethylaluminum solution diluted in n-hexane was continuously injected at a concentration of 20 moles of triethylaluminum per mole of neodymium. The first reactor was operated at a temperature of 0°C, and after 10 minutes of continuous injection, the mixture from the first reactor was transferred to the second reactor, into which a diisobutylaluminum hydride solution diluted in n-hexane was continuously injected at a concentration of 15 moles of diisobutylaluminum hydride per mole of neodymium. The second reactor was operated at a temperature of 0°C. After 30 minutes of continuous injection, the reactants from the second reactor were transferred to the third reactor, into which a diethylaluminum chloride solution diluted with n-hexane was continuously injected at a concentration of 3 moles of diethylaluminum chloride per 1 mole of neodymium. The third reactor was operated at a temperature of -5°C. After 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature below 0°C.

[0138] <Example 3> Three pressure-resistant reactors, each with a volume of 300 ml and equipped with jackets and stirrers, were connected in series and used as a continuous catalyst production reactor. A nitrogen atmosphere was maintained in each reactor. A neodymium versatate solution diluted in n-hexane was continuously injected into the first reactor, simultaneously with 1,3-butadiene diluted in n-hexane, and a triethylaluminum solution diluted in n-hexane was continuously injected at a concentration of 10 moles of triethylaluminum per mole of neodymium. The first reactor was operated at a temperature of 0°C, and after 10 minutes of continuous injection, the mixture from the first reactor was transferred to the second reactor, into which a diisobutylaluminum hydride solution diluted in n-hexane was continuously injected at a concentration of 15 moles of diisobutylaluminum hydride per mole of neodymium. The second reactor was operated at a temperature of 0°C. After 30 minutes of continuous injection, the reactants from the second reactor were transferred to the third reactor. To the third reactor, an ethyl aluminum sesquichloride solution diluted with n-hexane was continuously injected at a concentration of 2 moles of ethyl aluminum sesquichloride per 1 mole of neodymium. The third reactor was operated at a temperature of -5°C. After 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature below 0°C.

[0139] <Example 4> Three pressure-resistant reactors, each with a volume of 300 ml and equipped with jackets and stirrers, were connected in series and used as a continuous catalyst production reactor. A nitrogen atmosphere was maintained in each reactor. A neodymium versatate solution diluted in n-hexane was continuously injected into the first reactor, simultaneously with 1,3-butadiene diluted in n-hexane, and a triethylaluminum solution diluted in n-hexane was continuously injected at a concentration of 10 moles of triethylaluminum per mole of neodymium. The first reactor was operated at a temperature of 0°C, and after 10 minutes of continuous injection, the mixture from the first reactor was transferred to the second reactor, into which a triisobutylaluminum solution diluted in n-hexane was continuously injected at a concentration of 30 moles of triisobutylaluminum per mole of neodymium. The second reactor was operated at a temperature of 0°C. After 30 minutes of continuous injection, the reactants from the second reactor were transferred to the third reactor, into which a diethylaluminum chloride solution diluted with n-hexane was continuously injected at a concentration of 3 moles of diethylaluminum chloride per 1 mole of neodymium. The third reactor was operated at a temperature of -5°C. After 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature below 0°C.

[0140] <Comparative Example 1> Two pressure-resistant reactors, each with a volume of 300 ml and equipped with jackets and stirrers, were connected in series and used as a continuous catalyst production reactor. A nitrogen atmosphere was maintained in each reactor. A neodymium versatate solution diluted in n-hexane was continuously injected into the first reactor, simultaneously with a 1,3-butadiene solution diluted in n-hexane. A diisobutylaluminum hydride solution diluted in n-hexane was continuously injected at a concentration of 15 moles of diisobutylaluminum hydride per mole of neodymium. The first reactor was operated at a temperature of 0°C. After 30 minutes of continuous injection, the reactants from the first reactor were transferred to the second reactor. A diethylaluminum chloride solution diluted in n-hexane was continuously injected into the second reactor at a concentration of 3 moles of diethylaluminum chloride per mole of neodymium. The second reactor was operated at a temperature of -5°C. After 30 minutes of continuous injection, the prepared catalyst composition was collected in a pressure vessel prepared under a nitrogen atmosphere and stored at a temperature below 0°C.

[0141] <Comparative Example 2> Diluted 1,3-butadiene in n-hexane was added to the reactor, and neodymium versatate (manufactured by Solvay) was added. Next, diisobutylaluminum hydride was added to the reactor at a concentration of 15 moles per mole of neodymium at a temperature of 0°C and stirred for 30 minutes. Next, diethylaluminum chloride was added to the reactor at a concentration of 3 moles per mole of neodymium at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0142] <Comparative Example 3> Diluted 1,3-butadiene in n-hexane was added to the reactor, and neodymium versatate (Solvay) was added. Then, triisobutylaluminum was added to the reactor at a concentration of 30 moles of triisobutylaluminum per 1 mole of neodymium at a temperature of 0°C and stirred for 30 minutes. Next, diethylaluminum chloride was added to the reactor at a concentration of 3 moles of diethylaluminum chloride per 1 mole of neodymium at a temperature of -5°C and stirred for 30 minutes to produce the catalyst composition.

[0143] [Example of experiment] <Experimental Example 1: Production of conjugated diene polymers and evaluation of catalyst composition activity> 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 prepared in Examples 1 to 4, 0.01 g of diisobutylaluminum hydride was added as a molecular weight modifier. When using the catalyst compositions prepared in Comparative Examples 1 to 3, 0.25 g of diisobutylaluminum hydride was added as a molecular weight modifier. After adding the catalyst compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3, 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 (BAS) 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, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a butadiene polymer.

[0144] During the production of the butadiene polymer, a portion of the polymerization solution was taken 25 minutes after the start of polymerization, and the TSC (total solid content, %) was measured. The polymerization conversion rate was then calculated using the following mathematical formula 1. The polymerization conversion rate after 25 minutes was measured for each catalyst composition in Examples 1-4 and Comparative Examples 1-3 to evaluate the catalyst composition activity, which is shown in Table 1 below. The measured value for Comparative Example 2 was used as the baseline, and the catalyst composition activity of each example and comparative example was indexed using the following mathematical formula 2.

[0145] [Mathematical formula 1] Polymerization conversion rate (%) = TSC of the sample (%) / Concentration of 1,3-butadiene added (wt%)

[0146] [Mathematical formula 2] Activity Index = (Measured Value / Reference Value) × 100

[0147] [Table 1]

[0148] As shown in Table 1 above, it was confirmed that the catalyst compositions produced in Examples 1 to 4 exhibited significantly higher activity compared to Comparative Examples 1 to 3.

[0149] On the other hand, in Comparative Example 1, in which the pretreatment step using triethylaluminum 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 was lower compared to Examples 1 to 4, and in particular compared to Examples 1 and 2, which used the same alkylating agent and halogen compound.

[0150] Furthermore, in Comparative Example 2, in which the catalyst composition was produced using a batch reactor without performing a pretreatment step with triethylaluminum on the lanthanum-based rare earth element compound according to the present invention, it was confirmed that the activity of the catalyst composition was lower compared to Examples 1-4, and especially compared to Examples 1 and 2, which used the same alkylating agent and halogen compound.

[0151] Furthermore, in Comparative Example 3, in which the catalyst composition was produced using a batch reactor without performing a pretreatment step with triethylaluminum on the lanthanum-based rare earth element compound according to the present invention, even when the alkylating agent was changed to triisobutylaluminum and used in excess, the alkylation reaction was not carried out sufficiently. It was confirmed that the activity of the catalyst composition was lower compared to Examples 1-4, and especially compared to Example 4, which used the same alkylating agent and halogen compound.

[0152] <Experimental Example 2: Evaluation of the physical properties of conjugated diene polymers> For the conjugated diene polymers produced in Experimental Example 1 using the catalyst compositions of Examples 1 to 4 and Comparative Examples 1 to 3, the Mooney viscosity, molecular weight distribution, and cis-1,4 bond content were measured as follows and are shown in Table 2 below.

[0153] *Mooney viscosity (ML1+4, @100℃): For each polymer, the Mooney viscosity was measured using a Monsanto MV2000E with a Large Rotor at 100℃ with 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, filled into the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen.

[0154] *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. All newly replaced columns were mixed-bed type columns, and polystyrene was used as the GPC standard material.

[0155] *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, carbon disulfide from the same cell was used as a blank, and the FT-IR transmittance spectrum of a carbon disulfide solution of the conjugated diene polymer, prepared at a concentration of 5 mg / mL, was measured. Then, the 1130 cm⁻¹ of the measured spectrum was taken. -1 The maximum peak value in the vicinity, a (baseline), is 967 cm, indicating trans-1,4 coupling. -1 The smallest peak value in the vicinity, b, is 911 cm, indicating vinyl bonding. -1 The minimum peak value in the vicinity is c, and 736 cm² indicates a cis-1,4 bond. -1 The respective concentrations were determined using the nearest minimum peak value d.

[0156] [Table 2]

[0157] As shown in Table 2 above, it was confirmed that the conjugated diene polymers produced using the catalyst compositions manufactured in Examples 1 to 4 exhibited appropriate levels of Mooney viscosity and molecular weight distribution, and that a high level of cis-1,4 bond content could be ensured.

[0158] On the other hand, it was confirmed that the conjugated diene polymers produced using the catalyst compositions manufactured in Comparative Examples 1 to 3 had a lower cis-1,4 bond content and a wider molecular weight distribution compared to Examples 1 to 4.

[0159] <Experimental Example 3: Evaluation of the physical properties of rubber compositions> After producing rubber compositions and rubber test pieces using the catalyst compositions of Examples 1-4 and Comparative Examples 1-3, and the conjugated diene polymer produced in Experimental Example 1, the Mooney viscosity, abrasion resistance, tensile properties, and viscoelastic properties of the rubber compositions were measured using the following method and are shown in Table 3 below.

[0160] <Manufacturing of rubber compositions and rubber test specimens> Using the catalyst compositions of Examples 1-4 and Comparative Examples 1-3, the following were prepared by blending 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 with 100 parts by weight of the conjugated diene polymer produced in Experimental Example 1.

[0161] Next, 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.

[0162] *Tensile properties: After vulcanizing each of the manufactured rubber compositions at 150°C for 90 minutes, the modulus of the vulcanized product at 300% elongation (M-300%, kg·f / cm) was determined in accordance with ASTM D412. 2 The following values ​​were measured. The measured values ​​for Comparative Example 2 were used as the reference values, and the 300% modulus of each example and comparative example was indexed using the following mathematical formula 3.

[0163] [Mathematical formula 3] M - 300% Index = (Measured value / Reference value) × 100

[0164] *Viscoelastic properties: The viscoelastic coefficient (Tanδ) was measured at -60°C to 60°C using a DMTS 500N manufactured by Gabo GmbH, Germany, at a frequency of 10 Hz, with a prestrain of 3% and a dynamic strain of 3%. Here, the Tanδ value at 0°C indicates rolling resistance, and the Tanδ value at 60°C indicates rotational resistance characteristics (fuel efficiency). The measured value of Comparative Example 2 was used as the reference value, and the viscoelastic properties of each example and comparative example were indexed using the following mathematical formula 4.

[0165] [Mathematical formula 4] Tan δ 60℃ Index = (Reference Value / Measured Value) × 100

[0166] *Abrasion resistance: Each of the rubber test pieces manufactured 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 2 was used as the reference value, and the abrasion resistance of each example and comparative example was indexed using the following mathematical formula 5.

[0167] [Mathematical formula 5] Wear Index = (Reference Value / Measured Value) × 100

[0168] [Table 3]

[0169] As shown in Table 3 above, it was confirmed that the rubber compositions produced using the catalyst compositions manufactured in Examples 1 to 4, and containing the conjugated diene polymers, exhibited improved tensile properties, viscoelastic properties, and abrasion resistance compared to the rubber compositions produced using the catalyst compositions manufactured in Comparative Examples 1 to 3.

[0170] On the other hand, it was confirmed that the rubber composition produced using the catalyst composition produced in Comparative Example 1, 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 2.

[0171] These results stem from improved catalytic activity achieved by pre-treating the catalyst composition for producing conjugated diene polymers with hydrogen-bonded lanthanum rare earth compounds and / or oligomeric forms of lanthanum rare earth compounds, which cause a decrease in catalytic activity, before the alkylation reaction.

[0172] 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, before the alkylation reaction.

[0173] 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 lanthanum-based rare earth elements remaining within the polymer, 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. A pretreatment step (S10) in which a pretreatment reaction is carried out on a hydrogen-bonded lanthanum-based rare earth element compound, an oligomeric form of a lanthanum-based rare earth element compound, or a combination thereof, Step (S20) involves mixing the lanthanum-based rare earth element compound pretreated in step (S10) with an alkylating agent and reacting them, The process includes a halogenation reaction step (S30) in which the alkylated lanthanum-based rare earth element compound in step (S20) is mixed with a halogen compound and reacted, Step (S10) is carried out by mixing the lanthanum-based rare earth element compound with one or more trialkylaluminum selected from the group consisting of trimethylaluminum and triethylaluminum, and reacting them. The (S10) step is carried out by adding one or more trialkylaluminum selected from the group consisting of trimethylaluminum and triethylaluminum in a molar ratio of 1 mole to 20 moles per mole of the lanthanum-based rare earth element compound. Step (S20) is carried out by adding an alkylating agent in a molar ratio of 10 moles to 30 moles per mole of a pre-treated lanthanum-based rare earth element compound. The (S30) step is carried out by adding a halogen compound to 1 mole of the lanthanum-based rare earth element compound in a molar ratio of 0.1 moles to 5.0 moles. Steps (S10), (S20), and (S30) are carried out in separate reactors connected in series, The aforementioned lanthanum-based rare earth element compound is a neodymium compound represented by the following chemical formula 1, The alkylating agent is an alkylaluminum compound represented by the following chemical formula 2. A method for producing a catalyst composition. 【Transformation 5】 In the above chemical formula 1, R1 to R3 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, but R1 to R3 are not all hydrogen. [Chemical formula 2] AlR 4 R 5 R 6 In the above chemical formula 2, R4 to R6 are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms. However, if R4 to R6 are not all hydrogen atoms, and R4 to R6 are all alkyl groups, then the number of carbon atoms in the alkyl group is 3 to 12.

2. The method for producing the catalyst composition according to claim 1, wherein step (S10) is carried out at a temperature of -20°C or higher and 40°C or lower for 10 minutes or more and 1 hour or less.

3. 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.

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

5. A 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.

6. The method for producing the catalyst composition according to claim 1, wherein the halogen compound 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 and R 8 Each of these is an alkyl group having 1 to 4 carbon atoms, R 9 It is a halogen group, 【Transformation 6】 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.

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

8. The method for producing the catalyst composition according to claim 1, wherein steps (S10), (S20), and (S30) are carried out in succession.

9. 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, to produce an active polymer.

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