WO2018084579A1 - Modified conjugated diene-based polymer and method for preparing same - Google Patents

Abstract

The present invention relates to a modifier represented by chemical formula 1, a method for preparing same, a high- modification rate modified conjugated diene-based polymer comprising a functional group derived from the modifier, and a method for preparing the polymer.

Description

Modified conjugated diene polymer and preparation method thereof

[Citations with Related Applications]

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0146927 filed on Nov. 4, 2016 and Korean Patent Application No. 10-2017-0143946 filed on Oct. 31, 2017, The contents are included as part of this specification.

[Technical Field]

The present invention relates to a modifier represented by the formula (1), a method for preparing the same, a modified conjugated diene-based polymer having a high modification rate including a functional group derived from the modifier, and a method for preparing the polymer.

BACKGROUND ART In recent years, as the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers having low running resistance, excellent wear resistance, tensile characteristics, and adjustment stability represented by wet skid resistance.

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, a rebound elasticity of 50 ° C. to 80 ° C., tan δ, Goodrich heat generation and the like are used. That is, a rubber material having a high rebound elasticity at the above temperature or a small tan δ or good rich heat generation is preferable.

As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low wet skid resistance. Recently, conjugated diene-based (co) polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. .

In the case where the above BR or SBR is used as a rubber material for tires, fillers such as silica and carbon black are usually blended together in order to obtain required tire properties. However, the affinity between the BR or SBR and the filler is not good, but there is a problem in that physical properties including wear resistance, crack resistance, or processability are deteriorated.

Therefore, as a method for improving the dispersibility of fillers such as SBR and silica or carbon black, a method of modifying the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organolithium into a functional group capable of interacting with the filler has been proposed. . For example, a method of modifying the polymerizable active end of the conjugated diene polymer with a tin compound, introducing an amino group, or modifying an alkoxysilane derivative has been proposed.

Furthermore, in the living polymer obtained by coordination polymerization using the catalyst composition containing a lanthanum series rare earth element compound as a method for improving the dispersibility of BR and fillers, such as a silica and carbon black, A method of denaturation by denaturing agents has been developed.

However, the BR or SBR modified by the above-described method has a low terminal denaturation rate, so that the improvement of physical properties is insignificant in a tire manufactured using the same.

The present invention has been made to solve the problems of the prior art, and an object thereof is to provide a modifier useful for polymer modification.

Another object of the present invention is to provide a method for producing the modifier.

Still another object of the present invention is to provide a modified conjugated diene-based polymer having a high modification rate including the functional group derived from the modifier.

Furthermore, another object of the present invention is to provide a method for producing the modified conjugated diene polymer.

In order to solve the above problems, the present invention provides a modifier represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ ,

R ⁴ is a C 1-20 divalent hydrocarbon group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. ,

R ⁵ is a divalent hydrocarbon group having 2 to 20 carbon atoms,

R ⁶ is -COOR ¹⁰ ,

R ⁷ to R ⁹ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ¹⁰ is substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. to be.

In addition, the present invention comprises the steps of preparing a compound represented by the following formula (4) by first reacting the compound represented by the formula (2) and the compound represented by the formula (3) (step a); And it provides a method of producing the modifier represented by the formula (1) comprising the step (step b) of a second reaction of the compound represented by the formula (4) and the compound represented by the formula (5).

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

R ⁷ R ⁸ R ⁹ SiCl

[Formula 1]

In Chemical Formulas 1 to 5,

R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ ,

R ⁴ is a C 1-20 divalent hydrocarbon group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. ,

R ⁵ is a divalent hydrocarbon group having 2 to 20 carbon atoms,

R ⁶ is -COOR ¹⁰ ,

R ⁷ to R ⁹ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ¹⁰ is substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. to be.

In addition, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the formula (1).

Furthermore, the present invention comprises the steps of preparing an active polymer in which the organic metal is bonded by polymerizing a conjugated diene monomer in the presence of a catalyst composition comprising a lanthanum series rare earth element-containing compound in a hydrocarbon solvent (step 1); And it provides a method for producing the modified conjugated diene-based polymer comprising the step (step 2) of reacting the active polymer with a modifier represented by the formula (1).

The modifying agent represented by Formula 1 according to the present invention has a high anion reactivity due to the introduction of a polymer reactive functional group, such as an ester group, and thus can easily act with the active site of the polymer.

In addition, the modified conjugated diene-based polymer according to the present invention may be excellent in affinity with a filler such as carbon black by including a modifier-derived functional group represented by the formula (1).

In addition, the method for producing a modified conjugated diene-based polymer according to the present invention can easily prepare a modified conjugated diene-based polymer having a high modification rate by using a modifier represented by the formula (1).

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The present invention provides a modifier useful for the modification of the modified conjugated diene-based polymer.

According to another embodiment of the present invention, the denaturant is represented by the following Chemical Formula 1.

Modifier represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ ,

R ⁴ is a C 1-20 divalent hydrocarbon group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. ,

R ⁵ is a divalent hydrocarbon group having 2 to 20 carbon atoms,

R ⁶ is -COOR ¹⁰ ,

R ⁷ to R ⁹ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ¹⁰ is substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. to be.

Specifically, in Formula 1, R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are independently of each other having 1 to 20 carbon atoms. It may be a monovalent hydrocarbon group or a monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O.

When R ⁷ , R ⁸ and R ⁹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 20 carbon atoms. It may be selected from the group consisting of an alkyl group, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, specifically, R ⁷ , R ⁸ and R ⁹ are independently an alkyl group having 1 to 10 carbon atoms, It may be selected from the group consisting of a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms and an arylalkyl group having 7 to 12 carbon atoms.

In addition, when R ⁷ , R ⁸ and R ⁹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms containing a hetero atom, R ⁷ , R ⁸ and R ⁹ are independently of each other at least one carbon atom in the hydrocarbon group Instead it comprises a hetero atom; Alternatively, at least one hydrogen atom bonded to a carbon atom in the hydrocarbon group may be substituted with a hetero atom or a functional group including a hetero atom. Specifically, when R <^7> , R <^8> and R <^9> is a C1-C20 monovalent hydrocarbon containing a hetero atom independently from each other, an alkoxy group; Phenoxy group; Carboxyl groups; Acid anhydride groups; Amino group; Amide group; Epoxy groups; Mercapto group; -[R ¹¹ O] xR ¹² (wherein R ¹¹ is an alkylene group having 2 to 20 carbon atoms, R ¹² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms) And an arylalkyl group having 7 to 20 carbon atoms, and x is an integer of 2 to 10; C1-C20 monovalent hydrocarbon groups containing one or more functional groups selected from the group consisting of hydroxy groups, alkoxy groups, phenoxy, carboxyl groups, ester groups, acid anhydride groups, amino groups, amide groups, epoxy groups and mercapto groups (e.g. For example, it may be a hydroxyalkyl group, an alkoxyalkyl group, a phenoxyalkyl group, an aminoalkyl group or a thiolalkyl group. More specifically, when R ⁷ , R ⁸ and R ⁹ are independently of each other an alkyl group having 1 to 20 carbon atoms containing a hetero atom, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and having 7 to 20 carbon atoms a phenoxy group, a C 1 -C 20 amino-alkyl group and ^{- [R 11 O] xR 12} ( wherein R ¹¹ is an alkylene group having 2 to 10, and R ¹² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, having from 3 to It may be selected from the group consisting of 12 cycloalkyl groups, aryl groups having 6 to 18 carbon atoms and arylalkyl groups having 7 to 18 carbon atoms, x is an integer of 2 to 10).

In addition, in Formula 1, R ⁴ may be a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent hydrocarbon group having 1 to 20 carbon atoms substituted with a substituent.

When R ⁴ is a divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is an alkylene group having 1 to 10 carbon atoms such as methylene group, ethylene group or propylene group; Arylene groups having 6 to 20 carbon atoms such as a phenylene group and the like; Or an arylalkylene group having 7 to 20 carbon atoms as a combination group thereof. More specifically, R ⁴ may be an alkylene group having 1 to 10 carbon atoms. In addition, when R ⁴ is a divalent hydrocarbon group of 1 to 20 carbon atoms substituted with a substituent, R ⁴ is in the group consisting of an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms and an aryl group of 6 to 30 carbon atoms It may be an alkylene group having 1 to 10 carbon atoms substituted with one or more substituents selected.

In addition, in Formula 1, R ⁵ may be a divalent hydrocarbon group having 2 to 20 carbon atoms, specifically, may be an alkylene group having 2 to 10 carbon atoms.

In addition, in Chemical Formula 1, R ⁶ may be -COOR ¹⁰ , wherein R ¹⁰ is substituted with a substituent; Or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

When R ¹⁰ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms It may be selected from the group consisting of, specifically R ^{10 In} the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms and an arylalkyl group having 7 to 12 carbon atoms It may be selected.

In addition, when R ¹⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted with a substituent, one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms It may be an alkyl group having 1 to 10 carbon atoms substituted with the above substituents.

Specifically, in the formula 1, R ¹ , R ² and R ₃ are independently of each other -SiR ⁷ R ⁸ R ⁹ , R ⁴ and R ⁵ are independently of each other an alkylene group having 2 to 10 carbon atoms, R ⁶ is -COOR ¹⁰ , wherein R ⁷ to R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, and carbon atoms Alkoxyalkyl group having 2 to 10 carbon atoms, phenoxyalkyl group having 7 to 12 carbon atoms and aminoalkyl group having 1 to 10 carbon atoms, and R ¹⁰ is unsubstituted or substituted with 1 to 10 carbon atoms. It may be an alkyl group of 10 to 10.

More specifically, the denaturant represented by Chemical Formula 1 may be a compound represented by Chemical Formula 1-1 to Chemical Formula 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3, TMS represents a trimethylsilyl group.

The denaturant may be one having a solubility of at least 10 g in a nonpolar solvent such as 100 g of normal hexane at 25 ° C. and 1 atmosphere. Here, the solubility of the denaturant means the degree of clear dissolution without a hazy phenomenon when observed by the naked eye. Thus, the modifier according to an embodiment of the present invention can be used as a modifier for the polymer to improve the modification rate of the polymer.

In addition, the modifying agent represented by the formula (1) according to the present invention can be easily modified to a high modification rate of the conjugated diene polymer by including a reactive functional group, a filler affinity functional group and a solvent affinity functional group for the conjugated diene-based polymer In addition, it is possible to improve wear resistance, low fuel consumption characteristics, and workability of molded articles such as rubber compositions and tires prepared therefrom. Specifically, the denaturant of Chemical Formula 1 may include a reactive functional group (substituent corresponding to R ⁶ in Formula 1), an amine group, and an alkyl chain in the molecule as described above, wherein the reactive functional group is conjugated. By exhibiting high reactivity to the active site of the diene polymer, the conjugated diene polymer can be modified at a high denaturation rate, and as a result, a functional group substituted with the modifier can be introduced into the conjugated diene polymer at a high yield. In addition, the amine group may be further reacted with the conjugated diene-based polymer terminal to be converted into a primary or secondary amino group to further improve affinity with the filler, particularly carbon black. In addition, the alkyl chain may increase the solubility of the modifier by increasing the affinity for the polymerization solvent, thereby improving the modification rate for the conjugated diene polymer.

In addition, the present invention provides a method for producing a modifier represented by the following formula (1).

The preparation method according to an embodiment of the present invention comprises the steps of preparing a compound represented by the following formula (4) by first reacting the compound represented by the formula (2) and the compound represented by the formula (3) (step a); And a second reaction of the compound represented by Chemical Formula 4 with the compound represented by Chemical Formula 5 (step b).

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

R ⁷ R ⁸ R ⁹ SiCl

[Formula 1]

In Chemical Formulas 1 to 5, R ¹ to R ⁶ are as defined above.

The first reaction of step a is a step for preparing a compound represented by Formula 4, and may be performed by first reacting the compound represented by Formula 2 with the compound represented by Formula 3. In this case, the compound represented by Formula 2 and the compound represented by Formula 3 may be used in a stoichiometric ratio, specifically, the compound represented by Formula 2 and the compound represented by Formula 3 are 1: 1 to It may be used in a molar ratio of 1: 2. More specifically, the compound represented by Formula 2 and the compound represented by Formula 3 may be used in a molar ratio of 1: 1.

Here, the first reaction may be performed at a temperature range of 10 ℃ to 30 ℃.

The second reaction of step b is a step for preparing a denaturant represented by Formula 1, and may be performed by reacting the compound represented by Formula 4 with the compound represented by Formula 5. In this case, the compound represented by Formula 4 and the compound represented by Formula 5 may be used in a stoichiometric ratio, for example, the compound represented by Formula 4 and the compound represented by Formula 5 is 1: 2 to 1: It may be used in a molar ratio of 5, specifically, it may be used in a molar ratio of 1: 3.5. On the other hand, the second reaction may be performed at a temperature range of -10 ℃ to 20 ℃.

In addition, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1).

[Formula 1]

In Chemical Formula 1, R ¹ to R ⁶ are as defined above.

The modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared by reacting the active polymer to which the organic metal is bonded and the modifier represented by Formula 1 through the manufacturing method described below, the modified conjugated diene-based The polymer may be improved in physical properties by including a modifier-derived functional group represented by Chemical Formula 1.

Specifically, the modifier represented by Formula 1 may be as described above.

Specifically, the modified conjugated diene-based polymer may include a filler affinity functional group and a solvent affinity functional group by including a modifier-derived functional group represented by the formula (1), a rubber composition comprising the same, and a tire prepared therefrom. Wear resistance, low fuel consumption characteristics and workability of the molded article can be improved.

The modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 100,000 g / mol to 700,000 g / mol, specifically 120,000 g / mol to 500,000 g / mol.

In addition, the modified conjugated diene-based polymer may have a weight average molecular weight (Mw) of 300,000 g / mol to 1,200,000 g / mol, specifically 400,000 g / mol to 1,000,000 g / mol.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1.05 to 5.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention has a weight distribution range as described above when considering the good effect of balancing the mechanical properties, elastic modulus and processability of the rubber composition when applied to the rubber composition The average molecular weight and the number average molecular weight may be one that satisfies the conditions of the aforementioned range at the same time.

Specifically, the conjugated diene-based polymer may have a molecular weight distribution of 3.4 or less, a weight average molecular weight of 300,000 g / mol to 1,200,000 g / mol, and a number average molecular weight of 100,000 g / mol to 700,000 g / mol. More specifically, the polydispersity may be 3.2 or less, a weight average molecular weight of 400,000 g / mol to 1,000,000 g / mol, and a number average molecular weight of 120,000 g / mol to 500,000 g / mol.

Here, the weight average molecular weight and the number average molecular weight are polystyrene equivalent molecular weights respectively analyzed by gel permeation chromatography (GPC), and the molecular weight distribution (Mw / Mn) is also called polydispersity, and the weight average molecular weight (Mw) And the ratio (Mw / Mn) to the number average molecular weight (Mn).

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a polymer having a high linearity of the value of -S / R (stress / relaxation) at 0.7 ℃ or more. At this time, the -S / R represents a change in the stress (stress) in response to the same amount of strain generated in the material, it is an index indicating the linearity of the polymer. In general, the lower the -S / R value, the lower the linearity of the polymer. The lower the linearity, the higher the rolling resistance or rolling resistance when applied to the rubber composition. In addition, the degree of branching and molecular weight distribution of the polymer can be predicted from the value of -S / R. The lower the value of -S / R, the higher the degree of branching, the broader molecular weight distribution, and as a result, the processability of the polymer is excellent while the mechanical Characteristics are low.

The modified conjugated diene-based polymer according to an embodiment of the present invention has a high -S / R value of 0.7 or more at 100 ℃ as described above, when applied to the rubber composition may be excellent in resistance properties and fuel economy characteristics. Specifically, the -S / R value of the modified conjugated diene-based polymer may be 0.7 to 1.0.

Herein, the -S / R value was measured under a condition of 100 ° C and Rotor Speed 2 ± 0.02 rpm using a Mooney viscometer, for example, Large Rotor of Monsanto MV2000E. Specifically, the polymer is allowed to stand at room temperature (23 ± 5 ° C.) for at least 30 minutes, and then 27 ± 3 g is collected and filled into the die cavity, and the platen is operated to measure the Mooney viscosity while applying torque. The -S / R value was obtained by measuring the slope value of the Mooney viscosity change appearing as the torque was released.

In detail, the modified conjugated diene-based polymer may have a cis-1,4 bond content of 95% or more, more specifically 98% or more of the conjugated diene portion measured by Fourier transform infrared spectroscopy (FT-IR). Thus, the wear resistance, crack resistance and ozone resistance of the rubber composition may be improved when applied to the rubber composition.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% or less, more specifically 2% or less, as measured by Fourier transform infrared spectroscopy. When the vinyl content in the polymer exceeds 5%, there is a fear that the wear resistance, crack resistance, and ozone resistance of the rubber composition including the same deteriorate.

Here, the cis-1,4 bond content and vinyl content in the polymer by the Fourier Transform Infrared Spectroscopy (FT-IR) are conjugated diene polymers prepared at a concentration of 5 mg / mL by blanking carbon disulfide in the same cell. After measuring the FT-IR transmittance spectrum of the carbon disulfide solution, the maximum peak value (a, baseline) near 1130 cm ⁻¹ of the measurement spectrum, and the smallest peak near 967 cm ⁻¹ indicating a trans-1,4 bond Each content is determined using the value (b), the minimum peak value (c) near 911 cm ^-1 representing vinyl bonds, and the minimum peak value (d) near 736 cm ^-1 representing cis-1,4 bonds. I got it.

In addition, the present invention provides a method for producing a modified conjugated diene-based polymer comprising a modifier derived group represented by the formula (1).

The preparation method according to an embodiment of the present invention is a step of preparing an active polymer in which an organic metal is bound by polymerizing a conjugated diene monomer in a hydrocarbon composition in the presence of a catalyst composition comprising a lanthanum-based rare earth element-containing compound in a hydrocarbon solvent (step 1 ); And reacting the active polymer with a denaturant represented by Formula 1 below (step 2).

[Formula 1]

In Chemical Formula 1, R ¹ to R ⁶ is as defined above.

Step 1 is a step for preparing an active metal combined with an organic metal using a catalyst composition comprising a lanthanum-based rare earth element-containing compound, which is performed by polymerizing a conjugated diene monomer in the presence of the catalyst composition in a hydrocarbon solvent. Can be.

The conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.

The hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclo hexane, toluene, benzene, and xylene.

The catalyst composition may be used in an amount such that the lanthanum-based rare earth element-containing compound is 0.1 mmnol to 0.5 mmol based on 100 g of the total conjugated diene-based monomer, and specifically, the lanthanum-based rare earth element-containing compound is conjugated diene. It may be used in an amount such that 0.1 mmol to 0.4 mmol, more specifically 0.1 mmol to 0.25 mmol, based on 100 g of the total monomers.

The lanthanum-based rare earth element-containing compound is not particularly limited, but may be any one or two or more compounds of atomic number 57 to 71 rare earth metals such as lanthanum, neodymium, cerium, gadolinium or praseodymium, and more specifically, neodymium It may be a compound containing at least one selected from the group consisting of, lanthanum and gadolinium.

In addition, the lanthanum-based rare earth element-containing compound is a rare earth element-containing carboxylate (for example, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium acetate, neodymium gluconate, neodymium citrate, neodymium fumarate, Neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate and the like); Organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis (1-methylheptyl) phosphate, neodymium bis (2-ethylhexyl) Phosphates, 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 disyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate, and the like); Organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methylheptyl) phosphate or Neodymium (2-ethylhexyl) phosphinate, etc.); Carbamates (eg, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate, etc.); Dithio carbamate (for example, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithio carbamate or neodymium dibutyldithiocarbamate); Xanthogenates (e.g., neodymium methyl xanthogenates, neodymium ethyl xanthogenates, neodymium isopropyl xanthogenates, neodymium butyl xanthogenates, or neodymium benzyl xanthogenates); β-diketonate (eg, neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl acetonate, etc.); Alkoxides or allyl oxides (eg, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.); Halides or pseudo halides (such as neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); Oxyhalides (eg, neodymium oxyfluoride, neodymium oxy chloride, or neodymium oxy bromide, etc.); Or an organic lanthanum series rare earth element-containing compound containing at least one rare earth element-carbon bond (e.g., Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn (cyclooctatetraene), (C ₅ Me _{5) 2} LnR, LnR _3, Ln (allyl) _3, or Ln (allyl) ₂ Cl, etc., wherein wherein Ln is a rare earth metal element, R is a hydrocarbyl group a) and the like, any one or of which It may comprise two or more mixtures.

Specifically, the lanthanum-based rare earth element-containing compound may include a neodymium-based compound represented by the following formula (6).

[Formula 6]

In Formula 6, R _a to R _c may be independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided that R _a to R _c are not all hydrogen at the same time.

As a specific example, the neodymium compound may be Nd (neodecanoate) ₃ , Nd (2-ethylhexanoate) ₃ , Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl Decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd ( 2-ethyl-2-propyl decanoate) ₃ , Nd (2-ethyl-2-butyl decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2 -Butyl decanoate) ₃ , Nd (2-propyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate Ate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd (2-t-butyl decanoate) ₃ , Nd (2,2-diethyl octanoate) ₃ , Nd (2, 2-dipropyl octanoate) ₃ , Nd (2,2-dibutyl octanoate) ₃ , Nd (2,2-dihexyl octanoate) ₃ , Nd (2-ethyl-2-propyl octanoate ) ₃ , Nd (2-ethyl-2-hexyl octanoe Ite) ₃ , Nd (2,2-diethyl nonanoate) ₃ , Nd (2,2-dipropyl nonanoate) ₃ , Nd (2,2-dibutyl nonanoate) ₃ , Nd (2, 2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ can be at least one selected from the group consisting of.

As another example, the lanthanum-based rare earth element-containing compound is more specifically represented by Chemical Formula 6 in view of excellent solubility in a polymerization solvent, conversion into catalytic active species, and thus an effect of improving catalytic activity without concern for oligomerization. Wherein R _a is a linear or branched alkyl group having 4 to 12 carbon atoms, and R _b and R _c are independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R _b and R _c are neodymium compounds Can be.

More specifically, in Formula 6, R _a is a linear or branched alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R _b And R _c may not be hydrogen at the same time, specific examples include Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-di Butyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl decanoate) ₃ , Nd (2-ethyl-2-butyl decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-butyl decanoate) ₃ , Nd (2-propyl -2-hexyl decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate) ₃ , Nd (2-hexyl-2-octyl Decanoate) ₃ , Nd (2-t-butyl decanoate) ₃ , Nd (2,2-diethyl octanoate) ₃ , Nd (2,2-dipropyl octanoate) ₃ , Nd (2,2-dibutyl octanoate) ₃ , Nd (2,2-dihexyl octanoate) ₃ , Nd (2-ethyl-2 -Propyl octanoate) ₃ , Nd (2-ethyl-2-hexyl octanoate) ₃ , Nd (2,2-diethyl nonanoate) ₃ , Nd (2,2-dipropyl nonanoate) ₃ , Nd (2,2-dibutyl nonanoate) ₃ , Nd (2,2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl- 2-hexyl nonanoate) ₃ may be one or more selected from the group consisting of, and among these, the neodymium-based compound is Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate Eight) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , and Nd (2,2-dioctyl decanoate) ₃ It may be one or more selected.

More specifically, in Chemical Formula 6, R _a may be a linear or branched alkyl group having 6 to 8 carbon atoms, and R _b and R _c may be each independently an alkyl group having 2 to 6 carbon atoms.

As such, the neodymium-based compound represented by Chemical Formula 6 includes a carboxylate ligand including an alkyl group having various lengths of 2 or more carbon atoms at the α (alpha) position as a substituent, thereby inducing steric changes around the neodymium center metal. The entanglement of the liver can be blocked, and accordingly, there is an effect of suppressing oligomerization. In addition, such a neodymium-based compound has a high solubility in the polymerization solvent, the rate of neodymium is located in the central portion that is difficult to convert to the catalytic active species is reduced, there is a high conversion rate to the catalytic active species.

In addition, the solubility of the lanthanum-based rare earth element-containing compound according to an embodiment of the present invention may be about 4 g or more per 6 g of nonpolar solvent at room temperature (25 ° C.).

In the present invention, the solubility of the neodymium-based compound means the degree of clear dissolution without turbid phenomenon, it can exhibit excellent catalytic activity by showing such a high solubility.

In addition, the lanthanum-based rare earth element-containing compound according to an embodiment of the present invention may be used in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of the lanthanum series rare earth element-containing compound in the solvent with a Lewis base and storing it in a stable state for a long time. The Lewis base may be used in an amount of 30 mol or less, or 1 to 10 mol, for example, per mol of rare earth elements. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenylether, triethylamine, organophosphorus compound or monovalent or dihydric alcohol and the like.

Meanwhile, the catalyst composition may further include at least one of (a) an alkylating agent, (b) a halide, and (c) a conjugated diene monomer together with a lanthanum-based rare earth element-containing compound.

Hereinafter, the above-mentioned (a) alkylating agent, (b) halide, and (c) conjugated diene type monomer are divided and demonstrated concretely.

 (a) alkylating agents

The alkylating agent may serve as a cocatalyst composition as an organometallic compound capable of transferring a hydrocarbyl group to another metal. The alkylating agent can be used without particular limitation as long as it is usually used as an alkylating agent in the preparation of the diene polymer, and is soluble in a polymerization solvent, such as, for example, an organoaluminum compound, an organic magnesium compound, or an organolithium compound. It may be an organometallic compound containing.

Specifically, as the organoaluminum compound, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentyl Alkyl aluminum, such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; 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 Lide, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl- n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum Hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride or benzyl-n-octylaluminum hydride Dihydrocarbyl aluminum hydride; Hydrocarbyl aluminum dihydrides such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride or n-octylaluminum dihydride Hydrides; and the like. Examples of the organic magnesium compound include alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or dibenzyl magnesium, and the like. Examples of the organolithium compound include alkyl lithium compounds such as n-butyllithium.

In addition, the organoaluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting water with a trihydrocarbyl aluminum compound, and specifically, may be a linear aluminoxane of Formula 7a or a cyclic aluminoxane of Formula 7b.

[Formula 7a]

[Formula 7b]

In Formulas 7a and 7b, R is a monovalent organic group bonded to an aluminum atom through a carbon atom, and may be a hydrocarbyl group, and x and y are each independently an integer of 1 or more, specifically 1 to 100 More specifically, it may be an integer of 2 to 50.

More specifically, the aluminoxane is methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n Pentyl aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenyl aluminoxane or 2,6- Dimethylphenyl aluminoxane and the like, and any one or a mixture of two or more thereof may be used.

In addition, the modified methyl aluminoxane is a methyl group of methyl aluminoxane substituted with a modification group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms, specifically, may be a compound represented by the following formula (8).

[Formula 8]

In Formula 8, R is as defined above, m and n may be an integer of 2 or more independently of each other. In addition, in Chemical Formula 8, Me represents a methyl group.

Specifically, in Formula 8, R is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may be an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an allyl group or an alkynyl group having 2 to 20 carbon atoms, and more specifically, having 2 or more carbon atoms It is an alkyl group of 10 to 10, and may be an isobutyl group more specifically.

More specifically, the modified methyl aluminoxane may be obtained by substituting about 50 mol% to 90 mol% of the methyl group of methyl aluminoxane with the aforementioned hydrocarbon group. When the content of the substituted hydrocarbon group in the modified methylaluminoxane is within the above range, it is possible to promote the alkylation to increase the catalytic activity.

Such modified methylaluminoxane may be prepared according to a conventional method, specifically, may be prepared using alkyl aluminum other than trimethylaluminum and trimethylaluminum. In this case, the alkyl aluminum may be triisobutyl aluminum, triethyl aluminum, trihexyl aluminum, trioctyl aluminum, or the like, and any one or a mixture of two or more thereof may be used.

In addition, the catalyst composition according to an embodiment of the present invention is a 1 to 200 molar ratio, specifically 1 to 100 molar ratio, more specifically 3 to 20 molar ratio of the alkylating agent relative to 1 mole of the lanthanum-based rare earth element-containing compound. It may be to include. If the alkylating agent is included in an amount exceeding 200 molar ratio, it is not easy to control the catalytic reaction during the preparation of the polymer, and the excess alkylating agent may cause side reactions.

(b) halides

The halide is not particularly limited, and examples thereof include a halogen alone, an interhalogen compound, a hydrogen halide, an organic halide, a nonmetal halide, a metal halide, or an organometallic halide. One or more than one mixture may be used. In consideration of the excellent catalytic activity and thus the reactivity improving effect, any one or two or more mixtures selected from the group consisting of an organic halide, a metal halide and an organometallic halide may be used as the halide.

Examples of the halogen alone include fluorine, chlorine, bromine or iodine.

In addition, examples of the interhalogen compounds include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.

Further, the hydrogen halide may include hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide.

In addition, the organic halides include t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, tri Phenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propy Onyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called 'iodoform'), tetraiodomethane, 1-io Dopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane ('neopentyl urea ), 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, ethyltriio Dosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, methyl iodoformate and the like.

In addition, the non-metal halides include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl ₄ ), silicon tetrabromide , Arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon iodide, arsenic triiode, tellurium iodide, boron triiodide, phosphorus triiode, phosphorus oxyiodide or phosphorus iodide Can be mentioned.

Further, the metal halide may be tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony trichloride, 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 triiode, gallium iodide, indium trioxide, titanium iodide, zinc iodide, zinc iodide Germanium, tin iodide, tin iodide, antimony triiodide or magnesium iodide.

In addition, the organometallic halide may be dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride. Bromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, ethyl Magnesium 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, Diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum di iodide, ethyl aluminum di iodide, n-butyl aluminum di iodide, isobutyl aluminum di iodide, methyl aluminum sesquiyoda Dide, Ethyl aluminum sesqui iodide, Isobutyl aluminum sesqui iodide, Ethyl magnesium iodide, n-butyl magnesium iodide Isobutyl magnesium iodide, phenylmagnesium iodide, benzyl magnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin diyo And odide or di-t-butyltin diiodide.

In addition, the catalyst composition according to an embodiment of the present invention is 1 to 20 moles, more specifically 1 to 5 moles, more specifically 2 to the halide relative to 1 mole of the lanthanum-based rare earth element-containing compound Moles to 3 moles. If the halide is contained in excess of 20 molar ratios, the catalytic reaction may not be easily removed, and an excess of halide may cause side reactions.

In addition, the catalyst composition for preparing a conjugated diene polymer according to an embodiment of the present invention may include a non-coordinating anion-containing compound or a non-coordinating anion precursor compound instead of or together with the halide.

Specifically, in the compound containing the non-coordinating anion, the non-coordinating anion is a steric bulky anion that does not form a coordination bond with the active center of the catalyst system due to steric hindrance, and is a tetraarylborate anion or a tetraaryl fluoride Borate anions and the like. In addition, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation together with the above non-coordinating anion; It may include an ammonium cation such as an N, N-dialkyl aninium cation, or a counter cation such as a phosphonium cation. More specifically, the compound containing the non-coordinating anion is triphenyl carbonium tetrakis (pentafluoro phenyl) borate, N, N-dimethylanilinium tetrakis (pentafluoro phenyl) borate, triphenyl carbonium tetra Kiss [3,5-bis (trifluoromethyl) phenyl] borate, or N, N-dimethylanilinium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

In addition, as the non-coordinating anion precursor, as a compound capable of forming non-coordinating anions under reaction conditions, a triaryl boron compound (BE ₃ , where E is a pentafluorophenyl group or a 3,5-bis (trifluoromethyl) phenyl group or the like) The same strong electron-withdrawing aryl group).

(c) conjugated diene monomer

The catalyst composition may further include a conjugated diene monomer, and a prepolymerization catalyst composition in which a part of the conjugated diene monomer used in the polymerization reaction is premixed with the catalyst composition for polymerization. By using it in the form of, the catalyst composition activity can be improved and the conjugated diene polymer to be produced can be stabilized.

In the present invention, the "preforming" is a catalyst composition comprising a lanthanum-based rare earth element-containing compound, an alkylating agent and a halide, i.e., when diisobutylaluminum hydride (DIBAH) is included in the catalyst system. In addition, a small amount of conjugated diene-based monomers such as 1,3-butadiene is added to reduce the possibility of generating various catalyst compositions active species, and pre-polymerization is performed in the catalyst composition system with addition of 1,3-butadiene. It may mean. In addition, "premix" may refer to a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

In this case, the conjugated diene monomer used in the preparation of the catalyst composition may be a part of the amount used within the total amount of the conjugated diene monomer used in the polymerization reaction, for example, the lanthanum-based rare earth element-containing compound 1 It may be used to 1 to 100 moles, specifically 10 to 50 moles, or 20 to 50 moles per mole.

The catalyst composition according to an embodiment of the present invention is at least one of the above-described lanthanum-based rare earth element-containing compound and alkylating agent, halide and conjugated diene-based monomer in an organic solvent, specifically, a lanthanum-based rare earth element-containing compound, alkylating agent and halogen It can be prepared by sequentially mixing the cargo and optionally conjugated diene-based monomers. In this case, the organic solvent may be a nonpolar solvent which is not reactive with the above catalyst components. Specifically, the nonpolar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo Linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; Mixed solvents of aliphatic hydrocarbons having 5 to 20 carbon atoms such as petroleum ether, petroleum spirits, kerosene, and the like; Or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, or the like, and any one or a mixture of two or more thereof may be used. More specifically, the nonpolar solvent may be a linear, branched or cyclic aliphatic hydrocarbon or aliphatic hydrocarbon having 5 to 20 carbon atoms, and more specifically n-hexane, cyclohexane, or a mixture thereof. Can be.

In addition, the organic solvent may be appropriately selected depending on the kind of constituent materials constituting the catalyst composition, especially the alkylating agent.

Specifically, in the case of alkylaluminoxanes such as methylaluminoxane (MAO) or ethylaluminoxane, as an alkylating agent, an aromatic hydrocarbon solvent may be appropriately used because it is not easily dissolved in an aliphatic hydrocarbon solvent.

In addition, when modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon solvent may be appropriately used. In this case, since it is possible to implement a single solvent system with an aliphatic hydrocarbon solvent such as hexane which is mainly used as a polymerization solvent, it may be more advantageous for the polymerization reaction. In addition, the aliphatic hydrocarbon solvent can promote the catalytic activity, and by this catalytic activity can further improve the reactivity.

The organic solvent may be used in an amount of 20 mol to 20,000 mol, and more specifically, 100 mol to 1,000 mol, based on 1 mol of the lanthanum-based rare earth element-containing compound.

On the other hand, the polymerization of step 1 may be carried out using coordination anion polymerization, or by radical polymerization, specifically, may be bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, more specifically in solution It can be sum.

In addition, the polymerization may be carried out by any of batch and continuous methods. Specifically, the polymerization in Step 1 may be carried out by adding a conjugated diene monomer to the catalyst composition in an organic solvent and reacting.

Here, the organic solvent may be added to the amount of the organic solvent that can be used to prepare the catalyst composition, the specific kind may be as described above. In addition, the concentration of the monomer when using the organic solvent may be 3% by weight to 80% by weight, or 10% by weight to 30% by weight.

In addition, the polymerization may include a reaction terminator for completing a polymerization reaction such as polyoxyethylene glycol phosphate; Or additives such as antioxidants such as 2,6-di-t-butylparacresol may be used. In addition, additives, such as chelating agents, dispersants, pH adjusting agents, deoxygenants or oxygen scavengers, which are typically used to facilitate solution polymerization, may optionally be further used.

In addition, the polymerization may be elevated temperature polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization).

Here, the constant temperature polymerization refers to a polymerization method including a step of polymerizing with self-heating reaction without adding heat after the addition of the organometallic compound, and the temperature rising polymerization is a temperature by optionally applying heat after adding the organometallic compound The isothermal polymerization refers to a polymerization method of increasing the heat by adding heat after the addition of the organometallic compound or increasing the heat or taking away the heat to maintain a constant temperature of the polymerization product.

The polymerization may be performed at a temperature range of -20 ° C to 200 ° C, specifically, 20 ° C to 150 ° C, more specifically, to be performed for 15 minutes to 3 hours at a temperature range of 10 ° C to 120 ° C. Can be. If the temperature of the polymerization exceeds 200 ℃, it is difficult to fully control the polymerization reaction, there is a fear that the cis-1,4 bond content of the resulting diene-based polymer is lowered, if the temperature is less than -20 ℃ polymerization reaction There is a fear that the speed and efficiency are lowered.

Step 2 is a step of reacting the active polymer with a modifier represented by Chemical Formula 1 to prepare a modified conjugated diene-based polymer.

The modifier represented by Formula 1 may be as described above, and may be used in the reaction by mixing one or two or more kinds.

The modifying agent represented by Formula 1 may be used in an amount of 0.5 mol to 20 mol relative to 1 mol of the lanthanum-based rare earth element-containing compound in the catalyst composition. Specifically, the modifying agent represented by Formula 1 may be used in an amount of 1 to 10 mol based on 1 mol of the lanthanum-based rare earth element-containing compound in the catalyst composition. If the denaturant is used in an amount within the ratio range, it is possible to perform a modification reaction of optimum performance, thereby obtaining a conjugated diene polymer having a high modification rate.

The reaction of step 2 is a modification reaction for introducing a functional group into the polymer, it may be to perform the reaction for 1 minute to 5 hours at 0 ℃ to 90 ℃.

In addition, the modified conjugated diene-based polymer manufacturing method according to an embodiment of the present invention may be carried out by a batch polymerization (batch) or a continuous polymerization method comprising one or more reactors.

After completion of the modification reaction, an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) or the like can be added to the polymerization reaction system to stop the polymerization reaction. Thereafter, the modified conjugated diene-based polymer may be obtained through desolvent treatment or vacuum drying such as steam stripping to lower the partial pressure of the solvent through supply of steam. In addition, the reaction product obtained as a result of the above-described modification reaction may include an active polymer, which is not modified, together with the above-mentioned modified conjugated diene polymer.

The preparation method according to an embodiment of the present invention may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary after step 2 above.

Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a molded article prepared from the rubber composition.

The rubber composition according to an embodiment of the present invention is 0.1 to 100% by weight of the modified conjugated diene-based polymer, specifically 10 to 100% by weight, more specifically 20 to 90% by weight It may be to include. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, improvement effects such as abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, the modified conjugated diene copolymer may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight.

The rubber component may be natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more thereof may be used. have.

In addition, the rubber composition may include a 0.1 to 150 parts by weight of a filler with respect to 100 parts by weight of the modified conjugated diene-based polymer, the filler may be a silica-based, carbon black or a combination thereof. Specifically, the filler may be carbon carbon rack.

Although the carbon black filler is not particularly limited, for example, the nitrogen adsorption specific surface area (measured based on N ₂ SA, JIS K 6217-2: 2001) may be 20 m 2 / g to 250 m 2 / g. In addition, the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc / 100g to 200 cc / 100g. When the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² / g, the workability of the rubber composition may be lowered. If the carbon black has a specific surface area of less than 20 m ² / g, the reinforcing performance by the carbon black may be insignificant. In addition, when the DBP oil absorption of the carbon black exceeds 200 cc / 100 g, the workability of the rubber composition may be lowered. If the DBP oil absorption of the carbon black is less than 80 cc / 100 g, the reinforcing performance by the carbon black may be insignificant.

In addition, the silica is not particularly limited, but may be, for example, wet silica (silicate silicate), dry silica (silicate anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be a wet silica having the most remarkable effect of improving the fracture characteristics and a wet grip. In addition, the silica has a nitrogen adsorption specific surface area (N ₂ SA) of 120 m 2 / g to 180 m 2 / g, and CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 m 2 / g to 200 m 2 / g. When the nitrogen adsorption specific surface area of the silica is less than 120 m 2 / g, the reinforcing performance by silica may be deteriorated. When the nitrogen adsorption specific surface area is less than 180 m 2 / g, the workability of the rubber composition may be deteriorated. In addition, when the CTAB adsorption specific surface area of the silica is less than 100 m 2 / g, reinforcing performance by silica as a filler may be deteriorated, and when it exceeds 200 m 2 / g, the workability of the rubber composition may be deteriorated.

Meanwhile, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasul Feed, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

In addition, in the rubber composition according to one embodiment of the present invention, since the modified conjugated diene-based polymer in which a functional group having a high affinity with a filler is introduced into the active site as a rubber component, the amount of the silane coupling agent used It can be reduced than usual. Specifically, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the filler. When used in the above range, the gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, the silane coupling agent may be used in 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus may further include a vulcanizing agent.

The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the content range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.

In addition, the rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, in particular, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, when included in the content, it is possible to prevent the degradation of tensile strength, low heat generation (low fuel consumption) of the vulcanized rubber.

In addition, as the anti-aging agent, specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.

The molded article manufactured using the rubber composition may include a tire or a tire tread.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

Preparation Example 1

1) Preparation of a compound represented by formula (i)

46.5 g (400 mmol) of hexamethylenediamine and 400 ml of tetrahydrofuran (THF) were added to a 1 L round bottom flask, followed by the slow addition of 48.1 g (480 mmol, 1.2 eq) of ethyl acrylate. Thereafter, the reaction was stirred at room temperature for 12 hours, and after confirming that the hexamethylenediamine was completely consumed, the reaction was terminated and the solvent was removed under reduced pressure. Thereafter, 500 ml of normal hexane was filtered and concentrated to a celite pad to obtain a compound represented by the following formula (i) (yield 80%). ¹ H nuclear magnetic resonance spectroscopy data of the compound represented by the formula (i) are as follows.

(i)

(i)

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.13 (2H, q, J = 7.2 Hz), 2.86 (2H, td, J = 6.5 Hz, 1.5 Hz), 2.67 (2H, td, J = 7.0 Hz, 3.5 Hz), 2.59 (2H, td, J = 7.1 Hz, 3.2 Hz), 2.49 (2H, t, J = 6.5 Hz), 1.50-1.40 (4H, m), 1.35-1.29 (4H, m), 1.25 (3H, t, J = 7.3 Hz), 1.06 (3H, br, s).

2) Preparation of the compound represented by Chemical Formula 1-1

Into a 2 L round bottom flask, 86.1 g (398 mmol) of the compound represented by Formula (i) prepared in 1) were added, 600 ml of dichloromethane was added, and 181.2 g (1.79 mol, 4.5 eq) of triethylamine was added thereto. It was. Thereafter, after cooling to 0 ° C., 151.3 g (1.39 mol, 3.5 eq) of chlorotrimethylsilane was added slowly, and the reaction was performed for 12 hours while the reaction temperature was raised to room temperature. Thereafter, the reaction was terminated and the solvent was removed under reduced pressure. The remaining organics were dissolved in 800 ml of normal hexane, washed three times with 150 ml of acetonitrile, filtered using a celite pad, and concentrated to give a compound represented by the following Chemical Formula 1-1 (yield 45%). ¹ H nuclear magnetic resonance spectroscopic data of the obtained compound of Formula 1-1 are as follows.

[Formula 1-1]

In Chemical Formula 1-1, TMS represents a trimethylsilyl group.

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.11 (2H, q, J = 7.0 Hz), 3.06 (2H, t, J = 7.3 Hz), 2.71 (2H, t, J = 7.5 Hz), 2.67 ( 2H, td, J = 7.5 Hz, 1.0 Hz), 2.38 (2H, t, J = 7.5 Hz), 1.41-1.29 (4H, m), 1.26 (3H, t, J = 7.3 Hz), 1.21-1.11 ( 4H, m), 0.08 (18H, s), 0.03 (9H, s).

Preparation Example 2

1) Preparation of a compound represented by formula (i)

46.5 g (400 mmol) of hexamethylenediamine, 111.6 g of aluminum oxide, and 400 ml of tetrahydrofuran (THF) were added to a 1 L round bottom flask, followed by the slow addition of 48.1 g (480 mmol, 1.2 eq) of ethyl acrylate. Thereafter, the reaction was stirred at room temperature for 12 hours, and after confirming that the hexamethylenediamine was completely consumed, the reaction was terminated and the solvent was removed under reduced pressure. Thereafter, the resultant was filtered and concentrated using 500 ml of normal hexane in a celite pad to obtain a compound represented by the following Chemical Formula (i) (yield 95%). ¹ H nuclear magnetic resonance spectroscopy data of the compound represented by the formula (i) are as follows.

(i)

(i)

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.13 (2H, q, J = 7.2 Hz), 2.86 (2H, td, J = 6.5 Hz, 1.5 Hz), 2.67 (2H, td, J = 7.0 Hz, 3.5 Hz), 2.59 (2H, td, J = 7.1 Hz, 3.2 Hz), 2.49 (2H, t, J = 6.5 Hz), 1.50-1.40 (4H, m), 1.35-1.29 (4H, m), 1.25 (3H, t, J = 7.3 Hz), 1.06 (3H, br, s).

2) Preparation of the compound represented by Chemical Formula 1-1

Into a 2 L round bottom flask, 86.1 g (398 mmol) of the compound represented by Formula (i) prepared in 1) were added, 600 ml of dichloromethane was added, and 181.2 g (1.79 mol, 4.5 eq) of triethylamine was added thereto. It was. Thereafter, after cooling to 0 ° C., 151.3 g (1.39 mol, 3.5 eq) of chlorotrimethylsilane was added slowly, and the reaction was performed for 12 hours while the reaction temperature was raised to room temperature. Thereafter, the reaction was terminated and the solvent was removed under reduced pressure. The remaining organics were dissolved in 800 ml of normal hexane, washed three times with 150 ml of acetonitrile, filtered using a celite pad, and concentrated to obtain a compound represented by the following Chemical Formula 1-1 (yield 65%). ¹ H nuclear magnetic resonance spectroscopic data of the obtained compound of Formula 1-1 are as follows.

[Formula 1-1]

In Chemical Formula 1-1, TMS represents a trimethylsilyl group.

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.11 (2H, q, J = 7.0 Hz), 3.06 (2H, t, J = 7.3 Hz), 2.71 (2H, t, J = 7.5 Hz), 2.67 ( 2H, td, J = 7.5 Hz, 1.0 Hz), 2.38 (2H, t, J = 7.5 Hz), 1.41-1.29 (4H, m), 1.26 (3H, t, J = 7.3 Hz), 1.21-1.11 ( 4H, m), 0.08 (18H, s), 0.03 (9H, s).

Preparation Example 3

1) Preparation of the compound represented by formula (ii)

29.7 g (400 mmol) of 1,3-diaminopropane and 400 ml of tetrahydrofuran (THF) were added to a 1 L round bottom flask, followed by the slow addition of 48.1 g (480 mmol, 1.2 eq) of ethyl acrylate. Thereafter, the reaction was stirred at room temperature for 12 hours, and after confirming that 1,3-diaminopropane was completely consumed, the reaction was terminated and the solvent was removed under reduced pressure. Thereafter, the resultant was filtered and concentrated using 500 ml of normal hexane in a celite pad to obtain a compound represented by the following Formula (ii) (yield 85%). Nuclear magnetic resonance spectroscopy data of ¹ H of the compound represented by the formula (ii) are as follows.

(ii)

(ii)

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.13 (2H, q, J = 7.2 Hz), 2.86 (2H, td, J = 6.5 Hz, 1.5 Hz), 2.67 (2H, td, J = 7.0 Hz, 3.5 Hz), 2.59 (2H, td, J = 7.1 Hz, 3.2 Hz), 1.47 (2H, m), 1.25 (3H, t, J = 7.3 Hz), 1.06 (3H, br, s).

2) Preparation of the compound represented by Formula 1-2

63.8 g (398 mmol) of the compound represented by Formula (ii) prepared in 1) were added to a 2 L round bottom flask and 600 ml of dichloromethane was added, followed by 181.2 g (1.79 mol, 4.5 eq) of triethylamine. It was. Thereafter, after cooling to 0 ° C., 151.3 g (1.39 mol, 3.5 eq) of chlorotrimethylsilane was added slowly, and the reaction was performed for 12 hours while the reaction temperature was raised to room temperature. Thereafter, the reaction was terminated and the solvent was removed under reduced pressure. The remaining organics were dissolved in 800 ml of normal hexane, washed three times with 150 ml of acetonitrile, filtered using a celite pad, and concentrated to give a compound represented by the following formula 1-2 (yield 72%). ¹ H nuclear magnetic resonance spectroscopy data of the obtained compound of formula 1-2 are as follows.

[Formula 1-2]

In Formula 1-2, TMS represents a trimethylsilyl group.

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.11 (2H, q, J = 7.0 Hz), 3.06 (2H, t, J = 7.3 Hz), 2.71 (2H, t, J = 7.5 Hz), 2.67 ( 2H, td, J = 7.5 Hz, 1.0 Hz), 1.41 (4H, m), 1.26 (3H, t, J = 7.3 Hz), 0.08 (18H, s), 0.03 (9H, s).

Preparation Example 4

1) Preparation of the compound represented by formula (iii)

46.5 g (400 mmol) of hexamethylenediamine and 400 ml of tetrahydrofuran (THF) were added to a 1 L round bottom flask, followed by the slow addition of 61.5 g (480 mmol, 1.2 eq) of butyl acrylate. Thereafter, the reaction was stirred at room temperature for 12 hours, and after confirming that the hexamethylenediamine was completely consumed, the reaction was terminated and the solvent was removed under reduced pressure. Thereafter, the resultant was filtered and concentrated using 500 ml of normal hexane in a celite pad to obtain a compound represented by the following formula (iii) (yield 80%). The nuclear magnetic resonance spectroscopy data of ¹ H of the compound represented by the formula (iii) are as follows.

(iii)

(iii)

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.13 (2H, q, J = 7.2 Hz), 2.86 (2H, td, J = 6.5 Hz, 1.5 Hz), 2.67 (2H, td, J = 7.0 Hz, 3.5 Hz), 2.59 (2H, td, J = 7.1 Hz, 3.2 Hz), 2.49 (2H, t, J = 6.5 Hz), 1.55 (2H, m), 1.50-1.40 (6H, m), 1.35-1.29 (4H, m), 1.25 (3H, t, J = 7.3 Hz), 1.06 (3H, br, s).

2) Preparation of the compound represented by Formula 1-3

97.3 g (398 mmol) of the compound represented by Formula (iii) prepared in 1) were added to a 2 L round bottom flask, followed by addition of 600 ml of dichloromethane, and 181.2 g (1.79 mol, 4.5 eq) of triethylamine was added thereto. It was. Thereafter, after cooling to 0 ° C., 151.3 g (1.39 mol, 3.5 eq) of chlorotrimethylsilane was added slowly, and the reaction was performed for 12 hours while the reaction temperature was raised to room temperature. Thereafter, the reaction was terminated and the solvent was removed under reduced pressure. The remaining organics were dissolved in 800 ml of normal hexane, washed three times with 150 ml of acetonitrile, filtered using a celite pad, and concentrated to obtain a compound represented by the following formula 1-3 (yield 62%). ¹ H nuclear magnetic resonance spectroscopy data of the obtained compound of Formula 1-3 are as follows.

[Formula 1-3]

In Formula 1-3, TMS represents a trimethylsilyl group.

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.11 (2H, q, J = 7.0 Hz), 3.06 (2H, t, J = 7.3 Hz), 2.71 (2H, t, J = 7.5 Hz), 2.67 ( 2H, td, J = 7.5 Hz, 1.0 Hz), 2.38 (2H, t, J = 7.5 Hz), 1.56 (2H, m), 1.41-1.29 (6H, m), 1.26 (3H, t, J = 7.3 Hz), 1.21-1.11 (4H, m), 0.08 (18H, s), 0.03 (9H, s).

Comparative Production Example

46.5 g (400 mmol) of hexamethylenediamine and 400 ml of tetrahydrofuran (THF) were added to a 1 L round bottom flask, followed by the slow addition of 168.2 g (1.68 mol, 4.2 eq) of ethyl acrylate. Thereafter, the reaction was stirred at room temperature for 12 hours, and after confirming that the hexamethylenediamine was completely consumed, the reaction was terminated and the solvent was removed under reduced pressure. Thereafter, the mixture was filtered and concentrated using 1 L of normal hexane in a celite pad to obtain a compound represented by the following formula (iv) (yield 90%). The nuclear magnetic resonance spectroscopy data of ¹ H of the compound represented by the formula (iv) are as follows.

(iv)

(iv)

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.13 (8H, q), 2.67 (8H, t), 2.59 (8H, t), 2.49 (8H, t), 1.50-1.40 (4H, m), 1.35 -1.29 (4H, m), 1.25 (12H, t).

Example 1

900 g of 1,3-butadiene and 6.6 kg of normal hexane were added to a 20 L autoclave reactor, and the temperature inside the reactor was raised to 70 ° C. A catalyst composition prepared by the reaction of a 0.10 mmol hexane solution of neodymium compound, 0.89 mmol of diisobutylaluminum hydride (DIBAH), 0.24 mmol of diethylaluminum chloride, and 3.3 mmol of 1,3-butadiene was prepared. After addition to the reactor, the polymerization proceeded for 60 minutes. Thereafter, a hexane solution containing 0.23 mmol of the compound represented by Chemical Formula 1-1 prepared in Preparation Example 1 was added thereto, followed by a modification reaction at 70 ° C. for 30 minutes. After that, hexane solution containing 1.0 g of polymerization terminator and WINGSTAY, an antioxidant  33 g of (Eliokem SAS, France) dissolved in 30% by weight of hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified butadiene polymer.

Example 2

900 g of 1,3-butadiene and 6.6 kg of normal hexane were added to a 20 L autoclave reactor, and the temperature inside the reactor was raised to 70 ° C. A catalyst composition prepared by the reaction of a 0.10 mmol hexane solution of neodymium compound, 0.89 mmol of diisobutylaluminum hydride (DIBAH), 0.24 mmol of diethylaluminum chloride, and 3.3 mmol of 1,3-butadiene was prepared. After addition to the reactor, the polymerization proceeded for 60 minutes. Thereafter, a hexane solution containing 0.23 mmol of the compound represented by Formula 1-2 prepared in Preparation Example 3 was added thereto, followed by a modification reaction at 70 ° C. for 30 minutes. After that, hexane solution containing 1.0 g of polymerization terminator and WINGSTAY, an antioxidant  33 g of (Eliokem SAS, France) dissolved in 30% by weight of hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified butadiene polymer.

Example 3

900 g of 1,3-butadiene and 6.6 kg of normal hexane were added to a 20 L autoclave reactor, and the temperature inside the reactor was raised to 70 ° C. A catalyst composition prepared by the reaction of a 0.10 mmol hexane solution of neodymium compound, 0.89 mmol of diisobutylaluminum hydride (DIBAH), 0.24 mmol of diethylaluminum chloride, and 3.3 mmol of 1,3-butadiene was prepared. After addition to the reactor, the polymerization proceeded for 60 minutes. Thereafter, a hexane solution containing 0.23 mmol of the compound represented by Formula 1-3 prepared in Preparation Example 4 was added thereto, followed by a modification reaction at 70 ° C. for 30 minutes. After that, hexane solution containing 1.0 g of polymerization terminator and WINGSTAY, an antioxidant  33 g of (Eliokem SAS, France) dissolved in 30% by weight of hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified butadiene polymer.

Comparative Example 1

900 g of 1,3-butadiene and 6.6 kg of normal hexane were added to a 20 L autoclave reactor, and the temperature inside the reactor was raised to 70 ° C. A catalyst composition prepared by the reaction of a 0.10 mmol hexane solution of neodymium compound, 0.89 mmol of diisobutylaluminum hydride (DIBAH), 0.24 mmol of diethylaluminum chloride, and 3.3 mmol of 1,3-butadiene was prepared. After addition to the reactor, the polymerization proceeded for 60 minutes. Subsequently, the hexane solution containing 1.0 g of the polymerization terminator and the antioxidant WINGSTAY  33 g of (Eliokem SAS, France) dissolved in 30% by weight of hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll dried to remove the residual solvent and water to prepare a butadiene polymer.

Comparative Example 2

900 g of 1,3-butadiene and 6.6 kg of normal hexane were added to a 20 L autoclave reactor, and the temperature inside the reactor was raised to 70 ° C. A catalyst composition prepared by the reaction of a 0.10 mmol hexane solution of neodymium compound, 0.89 mmol of diisobutylaluminum hydride (DIBAH), 0.24 mmol of diethylaluminum chloride, and 3.3 mmol of 1,3-butadiene was prepared. After addition to the reactor, the polymerization proceeded for 60 minutes. Thereafter, a hexane solution containing 0.23 mmol of the compound represented by Formula iv prepared in Comparative Comparative Example was added thereto, followed by a modification reaction at 70 ° C. for 30 minutes. After that, hexane solution containing 1.0 g of polymerization terminator and WINGSTAY, an antioxidant  33 g of (Eliokem SAS, France) dissolved in 30% by weight of hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified butadiene polymer.

On the other hand, the neodymium compounds used in the above Examples and Comparative Examples used the same material.

Experimental Example 1

The physical properties of the modified or unmodified butadiene polymers prepared in Examples 1 to 3, Comparative Example 1, and Comparative Example 2 were measured by the following methods, and the results are shown in Table 1 below.

1) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution

Each polymer was dissolved in tetrahydrofuran (THF) for 30 minutes under 40 ° C., and then loaded on a gel permeation chromatography (GPC). In this case, two columns of PLgel Olexis brand name and one PLgel mixed-C column of Polymer Laboratories were used in combination. The newly replaced columns were all mixed bed type columns, and polystyrene was used as the gel permeation chromatography standard material (GPC Standard material).

2) Mooney viscosity and -S / R value

For each polymer, the Mooney viscosity (MV) was measured under conditions of Rotor Speed 2 ± 0.02 rpm at 100 ° C. using a Large Rotor with Monsanto MV2000E. At this time, the sample used was allowed to stand at room temperature (23 ± 3 ℃) for more than 30 minutes, 27 ± 3g was taken and filled into the die cavity, and the platen was operated to apply a torque to measure the Mooney viscosity.

In addition, the change of the Mooney viscosity which appeared while torque was loosened at the time of the measurement of the said Mooney viscosity was observed for 1 minute, and -S / R value was determined from the inclination value.

3) cis-1,4 bond content

Fourier transform infrared spectroscopy was performed on each polymer, and the content of cis-1,4 bond in the 1,4-polybutadiene was determined from the results.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Degeneration denaturalization denaturalization denaturalization Undenatured denaturalization GPC results Mn (x10 ⁵ g / mol) 2.6 2.6 2.7 2.4 3.0 Mw (x10 ⁵ g / mol) 8.7 8.0 8.3 7.9 8.8 Mw / Mn 3.2 3.0 3.1 3.2 3.3 MV (ML1 + 4, @ 100 ℃) (MU) 46 47 46 47 54 -S / R 0.741 0.750 0.749 0.729 0.730 Cis-1,4 bond content (%) 97.0 97.4 97.5 97.1 97.2

As shown in Table 1, the modified butadiene polymers of Examples 1 to 3 according to an embodiment of the present invention have an increased -S / R value compared to the unmodified or modified butadiene polymers of Comparative Examples 1 and 2. It was confirmed. Through this, it can be seen that the modified butadiene polymer according to an embodiment of the present invention has a high linearity.

Experimental Example 2

After preparing the rubber composition and the rubber specimens using the modified or unmodified butadiene polymers prepared in Examples 1 to 3, Comparative Example 1 and Comparative Example 2, the Mooney viscosity, tensile strength, 300% modulus, elongation and viscoelasticity were measured respectively. The results are shown in Table 2 below.

Specifically, the rubber composition is 70 parts by weight of carbon black, 100 parts by weight of each modified or unmodified butadiene polymer, 22.5 parts by weight of process oil, 2 parts by weight of antioxidant (TMDQ), zinc oxide (ZnO) 3 Each rubber composition was prepared by combining parts by weight and 2 parts by weight of stearic acid. Then, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ) and 0.5 parts by weight of vulcanization accelerator (DPG) were added to each of the rubber compositions, and vulcanized at 160 ° C. for 25 minutes to prepare a rubber specimen.

1) Mooney viscosity (ML1 + 4)

Each rubber specimen was measured using a large rotor with Monsanto MV2000E at 100 ° C. at a rotor speed of 2 ± 0.02 rpm.

2) Payney Effect (△ G ')

The difference between the G 'of the elastic modulus and the G' of the strain at 40% was measured at 28% of each uncrosslinked rubber specimen. In this case, the smaller the value, the better the dispersibility of the carbon black.

3) tensile strength (kg · f / cm ² ), and 300% modulus (300% modulus, kg · f / cm ² )

After the rubber composition was vulcanized at 150 ° C. for t90 minutes, tensile strength of the vulcanizate, modulus at 300% elongation (M-300%), and elongation at break were measured according to ASTM D412.

4) Viscoelastic (Tanδ @ 60 ℃)

Tan δ properties, which are most important for low fuel efficiency, were measured using a Gabo DMTS 500N from Germany and measured viscoelastic modulus (tan δ) at 60 ° C at a frequency of 10 Hz, Prestrain 3% and Dynamic Strain 3%. At this time, the higher the value of δ, the less the hysteresis loss, the better the low rotational resistance, that is, the better fuel economy.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 ML1 + 4 (FMB: Final Master batch 70.1 69.1 67.5 62.0 75.5 Payney Effect (△ G ') 0.59 0.53 N / A 0.68 N / A Tensile Properties M-300% 96.9 98.0 96.5 92.4 103.4 The tensile strength 171 176 169 163 178 Elongation 453 468 445 461 423 tanδ @ 60 ℃ 0.143 0.141 0.139 0.155 0.152

In Table 2, N / A is not measured.

As shown in Table 2, the tensile and viscoelastic properties of the rubber specimens prepared using the modified butadiene polymers of Examples 1 to 3 prepared using the modifier according to the embodiment of the present invention are Comparative Example 1 And it was confirmed that compared with the rubber specimen prepared using the modified or unmodified butadiene polymer of Comparative Example 2.

Specifically, a rubber specimen prepared using the modified butadiene polymers of Examples 1 and 2 prepared using the modifier according to an embodiment of the present invention was prepared using the unmodified butadiene polymer of Comparative Example 1 It was confirmed that the Payne effect value is reduced compared to the rubber specimen. This indicates that the modified butadiene polymer prepared using the modifier according to the embodiment of the present invention has excellent affinity with carbon black.

In addition, a rubber specimen prepared using the modified butadiene polymers of Examples 1 to 3 prepared using the modifier according to an embodiment of the present invention is a rubber prepared using the unmodified butadiene polymer of Comparative Example 1 It was confirmed that the Tan δ value at 60 ℃ compared to the specimen. This is a result showing that the modified butadiene polymer prepared by using the modifier according to the embodiment of the present invention has excellent rolling resistance (RR) characteristics and high fuel efficiency.

In addition, the rubber specimens prepared using the modified butadiene polymers of Examples 1 to 3 prepared using the modifying agent according to an embodiment of the present invention have an increased elongation compared to the modified butadiene polymer of Comparative Example 2 at 60 ° C. It was confirmed that the Tan δ value of, and thus the modified butadiene polymer of Examples 1 to 3 is superior to the modified butadiene polymer of Comparative Example 2, it is confirmed that the rolling resistance (RR) characteristics and the fuel efficiency can be high. It was. In this case, the modified butadiene polymer of Comparative Example 2 is prepared by using a modifier having a tertiary amine group and an ester group, but no alkylsilane group, and having two or more ester groups, as in the modifier of the present invention.

Claims (20)

Modifier represented by the following formula (1): [Formula 1]

In Chemical Formula 1, R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ , R ⁴ is a C 1-20 divalent hydrocarbon group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. , R ⁵ is a divalent hydrocarbon group having 2 to 20 carbon atoms, R ⁶ is -COOR ¹⁰ , R ⁷ to R ⁹ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O, R ¹⁰ is substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. to be. The method according to claim 1, In Chemical Formula 1, R ¹ , R ² and R ₃ are independently of each other -SiR ⁷ R ⁸ R ⁹ , R ⁴ and R ⁵ are independently of each other an alkylene group having 2 to 10 carbon atoms, R ⁶ is -COOR ¹⁰ , R ⁷ to R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, It is any one selected from the group consisting of a phenoxyalkyl group having 7 to 12 carbon atoms and an aminoalkyl group having 1 to 10 carbon atoms, R ¹⁰ is a denaturing agent which is an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. The method according to claim 1, The modifier represented by Formula 1 is a compound represented by the following Formulas 1-1 to 1-3: [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3, TMS is a trimethylsilyl group. The method according to claim 1, The modifier is a modifier for a conjugated diene polymer. Preparing a compound represented by Chemical Formula 4 by first reacting the compound represented by Chemical Formula 2 with the compound represented by Chemical Formula 3; And A method for preparing a denaturant according to claim 1 represented by Chemical Formula 1, comprising the step of reacting a compound represented by Chemical Formula 4 with a compound represented by Chemical Formula 5 below: [Formula 2]

[Formula 3]

[Formula 4]

[Formula 5] R ⁷ R ⁸ R ⁹ SiCl [Formula 1]

In Chemical Formulas 1 to 5, R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ , R ⁴ is a C 1-20 divalent hydrocarbon group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. , R ⁵ is a divalent hydrocarbon group having 2 to 20 carbon atoms, R ⁶ is -COOR ¹⁰ , R ⁷ to R ⁹ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O, R ¹⁰ is substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. to be. The method according to claim 5, In Chemical Formulas 1 to 5, R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ , R ⁴ and R ⁵ are independently of each other an alkylene group having 2 to 10 carbon atoms, R ⁶ is -COOR ¹⁰ , R ⁷ to R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, It is any one selected from the group consisting of a phenoxyalkyl group having 7 to 12 carbon atoms and an aminoalkyl group having 1 to 10 carbon atoms, R ¹⁰ is an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, n is an integer of 0 to 8. The method according to claim 5, The compound represented by the formula (2) and the compound represented by the formula (3) is a method of producing a modifier that is reacted in a molar ratio of 1: 1 to 1: 2. The method according to claim 5, The compound represented by the formula (4) and the compound represented by the formula (5) is a method for producing a modifier that is reacted in a molar ratio of 1: 2 to 1: 5. The method according to claim 5, The first reaction is a method of producing a modifier that is carried out in a temperature range of 10 ℃ to 30 ℃. The method according to claim 5, The second reaction is a method of producing a denaturant is carried out at a temperature range of -10 ℃ to 20 ℃. Modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the formula (1): [Formula 1]

In Chemical Formula 1, R ¹ , R ² and R ³ are independently of each other -SiR ⁷ R ⁸ R ⁹ , R ⁴ is a C 1-20 divalent hydrocarbon group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. , R ⁵ is a divalent hydrocarbon group having 2 to 20 carbon atoms, R ⁶ is -COOR ¹⁰ , R ⁷ to R ⁹ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O, R ¹⁰ is substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. to be. The method according to claim 11, A modified conjugated diene-based polymer, wherein the modifying agent represented by Formula 1 is a compound represented by the following Formulas 1-1 to 1-3: [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3, TMS is a trimethylsilyl group. The method according to claim 11, The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 100,000 g / mol to 700,000 g / mol.  The method according to claim 11, The polymer is a modified conjugated diene-based polymer having a molecular weight distribution (Mw / Mn) of 1.05 to 5. The method according to claim 11, The polymer is a modified conjugated diene-based polymer that the value of -S / R (stress / relaxation) at 100 ℃ is 0.7 or more. 1) polymerizing a conjugated diene-based monomer in the presence of a catalyst composition comprising a lanthanum-based rare earth element-containing compound in a hydrocarbon solvent to prepare an active polymer having an organic metal bound thereto; And 2) A method for preparing a modified conjugated diene polymer according to claim 13 comprising the step of reacting the active polymer with a modifier represented by the following formula (1): [Formula 1]

In Chemical Formula 1, R^One, R² And R³Independently of each other -SiR⁷R⁸R⁹ego, R ⁴ is a C 1-20 divalent hydrocarbon group unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. , R ⁵ is a divalent hydrocarbon group having 2 to 20 carbon atoms, R ⁶ is -COOR ¹⁰ , R ⁷ to R ⁹ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O, R ¹⁰ is substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. to be. The method according to claim 16, The catalyst composition is a method for producing a modified conjugated diene-based polymer is used in an amount such that the lanthanum-based rare earth element-containing compound is 0.1 mmol to 0.5 mmol based on 100 g of the conjugated diene monomer. The method according to claim 16, The lanthanum-based rare earth element-containing compound is a method for producing a modified conjugated diene-based polymer comprising a neodymium-based compound represented by the following formula (6): [Formula 6]

In Chemical Formula 6, R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, Provided that both R _a to R _c are not simultaneously hydrogen. The method according to claim 18, The neodymium compounds include Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2 , 2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl decanoate) ₃ , Nd (2-ethyl-2-butyl de Decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-butyl decanoate) ₃ , Nd (2-propyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd (2, 2-diethyl octanoate) ₃ , Nd (2,2-dipropyl octanoate) ₃ , Nd (2,2-dibutyl octanoate) ₃ , Nd (2,2-dihexyl octanoate) ₃ , Nd (2-ethyl-2-propyl octanoate) ₃ , Nd (2-ethyl-2-hexyl octanoate) ₃ , Nd (2,2-diethyl nonanoate) ₃ , Nd (2, 2-dipropyl-no nano-benzoate) _3, Nd (2,2- dibutyl no nano Agent) _3, Nd (2,2- dihexyl no nano-benzoate) _3, Nd (2- ethyl-2-propyl-no nano-benzoate) ₃ and Nd (2- ethyl-2-hexyl-no nano-benzoate) the group consisting of ₃ Method for producing a modified conjugated diene-based polymer that is one or more selected from. The method according to claim 16, The modifying agent is a method for producing a modified conjugated diene-based polymer that is used in a ratio of 0.5 mol to 20 mol based on 1 mol of the lanthanum-based rare earth element-containing compound.