KR20200086532A - Modified conjugated diene polymer, preparation method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer having improved blending properties due to excellent affinity with a filler, a method for preparing the same, and a rubber composition comprising the same. The modified conjugated diene-based polymer may have excellent affinity with a filler because a functional group derived from a modifier represented by chemical formula 1 is bonded to a polymer side chain, and thus can be applied to a rubber composition to have excellent processability and excellent blending properties such as tensile properties, abrasion resistance, and viscoelastic properties.

Description

Modified conjugated diene polymer, a method of manufacturing the same, and a rubber composition comprising the same {Modified conjugated diene polymer, preparation method thereof and a rubber composition comprising the same}

The present invention relates to a modified conjugated diene-based polymer having improved affinity for fillers and improved formulation properties, a method for manufacturing the same, and a rubber composition comprising the same.

Recently, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene-based polymer is required as a rubber material for tires, which has low running resistance, excellent abrasion resistance and tensile properties, and also has 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, and as the evaluation index of the vulcanized rubber, repulsive elasticity of 50°C to 80°C, tan δ, and good-rich heat are used. That is, a rubber material having high rebound resilience at the above temperature or low tan δ or Goodrich heat generation is preferable.

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

When the BR or SBR is used as a rubber material for tires, a filler such as silica or carbon black is usually blended together to obtain the required tire properties. However, since the affinity between the BR or SBR and the filler is not good, there is a problem in that physical properties, such as wear resistance, crack resistance or workability, are deteriorated.

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

In addition, in the living polymer obtained by coordination polymerization using a catalyst composition containing a lanthanum-based rare earth element compound as a method for increasing the dispersibility of BR and fillers such as silica and carbon black, the living active terminal is determined by a specific modifier. A method of denaturation was developed. However, in the case of a polymer having a modified terminal, there is an advantage in that the affinity with the filler is improved, thereby improving the compounding properties, such as tensile and viscoelastic properties, whereas on the other hand, the compounding processability is greatly reduced, resulting in poor processability.

In addition, when the rubber composition tank is prepared by mixing SBR or BR with a filler such as silica or carbon black, a coupling agent having a functional group such as a silane group, an amine group or an azo group is mixed together to increase the affinity between the SBR or BR and the filler. Although the dispersibility of the filler was increased to improve the compounding properties and processability, the effect of improving the compounding properties was not obtained.

Therefore, in the case of SBR or BR production, there is a need for a method capable of improving processability while having excellent compounding properties.

JP 5172663 B2

The present invention has been devised to solve the problems of the prior art, and has an object to provide a modified conjugated diene-based polymer having excellent processability and improved compoundability.

In addition, an object of the present invention is to provide a method for producing the modified conjugated diene-based polymer.

In addition, an object of the present invention is to provide a rubber composition comprising the modified conjugated diene-based polymer.

In order to solve the above problems, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or a monovalent heterohydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O, R ₂ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms and a carbon number A divalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of 6 to 20 aryl groups; Or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O, and R ₃ to R ₅ are each independently an alkyl group having 1 to 20 carbon atoms or 1 to 1 carbon atom. It is an alkoxy group of 20, but at least one of R ₃ to R ₅ is an alkoxy group having 1 to 20 carbon atoms.

In addition, the present invention comprises the steps of polymerizing the conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent to prepare an active polymer (step 1); And reacting the active polymer with a modifier represented by Chemical Formula 1 (step 2) to provide a method for preparing the modified conjugated diene-based polymer.

[Formula 1]

In Chemical Formula 1,

R ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or a monovalent heterohydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O, R ₂ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms and a carbon number A divalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of 6 to 20 aryl groups; Or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O, and R ₃ to R ₅ are each independently an alkyl group having 1 to 20 carbon atoms or 1 to 1 carbon atom. It is an alkoxy group of 20, but at least one of R ₃ to R ₅ is an alkoxy group having 1 to 20 carbon atoms.

In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.

The modified conjugated diene-based polymer according to the present invention may have excellent affinity with a filler by bonding a functional group derived from a modifier represented by Formula 1 to a polymer chain side chain, and thus applied to a rubber composition, having excellent processability and tensile properties And viscoelastic properties.

In addition, the method for preparing the modified conjugated diene-based polymer according to the present invention is a functional group derived from a modifier in the polymer side chain due to the reaction of the double bond in the active polymer and the azo group in the modifier by denaturing the active polymer using the modifier represented by Formula 1 It is possible to easily prepare a modified conjugated diene-based polymer having a structure in which is bound.

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

The terms or words used in the specification and claims should not be interpreted as being limited to ordinary or dictionary meanings, and the inventor can appropriately define the concept of terms in order to best describe his or her invention. Based on the principle of being present, it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.

The term'substitution' used in the present invention may mean that hydrogen of a functional group, atomic group or compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group or compound is substituted with a specific substituent, present in a functional group, atomic group or compound One or two or more substituents may be present depending on the number of hydrogens. In addition, when a plurality of substituents are present, the respective substituents may be the same or different from each other.

The term'monovalent hydrocarbon group' used in the present invention refers to a monovalent substituent derived from a hydrocarbon group, such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group having one or more unsaturated bonds, and an aryl group. Carbon and hydrogen may represent a monovalent atomic group, and the monovalent atomic group may have a linear or branched structure depending on the structure of the bond.

The term'divalent hydrocarbon group' used in the present invention refers to a divalent substituent derived from a hydrocarbon group, such as an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, cycloalkyl containing one or more unsaturated bonds Carbon and hydrogen, such as an alkylene group and an arylene group, may represent a divalent atomic group, and the divalent atomic group may have a linear or branched structure depending on the structure of the bond.

The term'heterohydrocarbon group' used in the present invention is a substituent in which at least two different atoms are present among the atoms constituting the hydrocarbon group, for example, it may mean a hydrocarbon group containing at least one hetero atom among N, S and O. .

The term'alkyl group (alkyl group)' used in the present invention may mean a monovalent saturated aliphatic hydrocarbon, linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, secbutyl (sec-butyl) ), tertiary butyl (tert-butyl) and neo-pentyl (neo-pentyl), and the like.

The term'cycloalkyl group (cycloaklyl group)' used in the present invention may mean a cyclic saturated hydrocarbon.

The term'aryl group' used in the present invention may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon formed with one ring or a polycyclic aromatic hydrocarbon combined with two or more rings aromatic hydrocarbon).

The term'alkylene group' used in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

The terms'derived unit' and'derived functional group' used in the present invention may refer to a component, a structure originating from a substance, or the substance itself.

The present invention provides a modified conjugated diene-based polymer having excellent compoundability such as tensile properties, abrasion resistance, and viscoelastic properties while having excellent blendability.

Specifically, the modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that it contains a functional group derived from a modifier represented by the following Chemical Formula 1.

[Formula 1]

In Chemical Formula 1,

R ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or a monovalent heterohydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O, R ₂ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms and a carbon number A divalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of 6 to 20 aryl groups; Or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O, and R ₃ to R ₅ are each independently an alkyl group having 1 to 20 carbon atoms or 1 to 1 carbon atom. It is an alkoxy group of 20, but at least one of R ₃ to R ₅ is an alkoxy group having 1 to 20 carbon atoms.

The modifier according to the present invention may be the compound itself represented by the formula (1), or may include other compounds capable of modifying the conjugated diene-based polymer together with the compound represented by the formula (1).

Specifically, in Chemical Formula 1, R ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O. Can be

When R ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ₁ is 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 ₁ is 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 ₁ is a monovalent heterohydrocarbon group having 1 to 20 carbon atoms containing a hetero atom, R ₁ includes a hetero atom in place of one or more carbon atoms in a hydrocarbon group; Alternatively, one or more hydrogen atoms bonded to a carbon atom in a hydrocarbon group may be substituted with a hetero atom or a hetero atom-containing functional group, wherein the hetero atom may be selected from the group consisting of N, O and S. Specifically, if a monovalent hydrocarbon group having 1 to 20 carbon atoms in which the R ₁ include a hetero atom, and an alkoxy group; Phenoxy group; Carboxy group; Acid anhydride; Amino group; Amide group; Epoxy groups; Mercapto group; -[R ¹¹ O]xR ¹² (where 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, 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); A monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one functional group selected from the group consisting of hydroxy group, alkoxy group, phenoxy group, carboxy group, ester group, acid anhydride group, amino group, amide group, epoxy group and mercapto group. 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 ¹ is 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, a phenoxyalkyl group having 7 to 20 carbon atoms, and 1 to 20 carbon atoms. Aminoalkyl group of 20 and -[R ¹¹ O]xR ¹² (where R ¹¹ is an alkylene group having 2 to 10 carbon atoms, R ¹² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, 6 carbon atoms It may be selected from the group consisting of aryl groups of 18 to 18 and arylalkyl groups of 7 to 18 carbon atoms, x is an integer of 2 to 10).

Specifically, R ₁ may be a monovalent hydrocarbon group having 1 to 20 carbon atoms that does not contain a hetero atom.

In addition, in Chemical Formula 1, R ₂ is 1 to 20 carbon atoms 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 20 carbon atoms. Divalent hydrocarbon group; Or it may be a divalent heterohydrocarbon 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 ₂ is an unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, or a propylene group; An arylene group having 6 to 20 carbon atoms such as a phenylene group; Or a combination of these may be an arylalkylene group having 7 to 20 carbon atoms. Specifically, R ₂ may be an alkylene group having 1 to 10 carbon atoms.

In addition, when R ₂ 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 20 carbon atoms, R ₂ is 1 to 10 carbon atoms. It may be an alkylene group having 1 to 10 carbon atoms substituted with one or more substituents selected from the group consisting of an alkyl group, a cycloalkyl group having 3 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms.

In addition, when the R ₂ is C 1 -C 20 divalent heterocyclic hydrocarbon group containing a hetero atom, wherein R ₂ is to contain a heteroatom in place of one or more carbon atoms in the hydrocarbon group; Alternatively, one or more hydrogen atoms bonded to a carbon atom in a hydrocarbon group may be substituted with a hetero atom or a hetero atom-containing functional group, wherein the hetero atom may be selected from the group consisting of N, O and S.

Specifically, when R ₂ is a divalent hydrocarbon group having 1 to 20 carbon atoms containing a hetero atom, an alkoxy group; Phenoxy group; Carboxy group; Acid anhydride; Amino group; Amide group; Epoxy groups; Mercapto group; Alkylene group having 1 to 10 carbon atoms and 6 to 20 carbon atoms containing at least one functional group selected from the group consisting of hydroxy group, alkoxy group, phenoxy group, carboxy group, ester group, acid anhydride group, amino group, amide group, epoxy group and mercapto group. It may be an arylene group or an arylalkylene group having 7 to 20 carbon atoms.

In addition, in Formula 1, R ₃ to R ₅ may be each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. Specifically, R ₃ to R ₅ may be independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

In addition, in Chemical Formula 1 according to an embodiment of the present invention, R ₁ is 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, or 2 carbon atoms. It is any one selected from the group consisting of an alkoxyalkyl group of 10 to 10 and a phenoxyalkyl group of 7 to 12 carbon atoms, R ₂ is an alkylene group of 1 to 10 carbon atoms, R ₃ to R ₅ are each independently of 1 to 10 carbon atoms. It may be an alkyl group or an alkoxy group having 1 to 10 carbon atoms.

As a specific example, the modifier represented by Chemical Formula 1 may be one or more selected from the group consisting of compounds represented by Chemical Formulas 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

The denaturing agent according to an embodiment of the present invention may include an ester group, an azo group, a carboxyl group, a nitroxyl group, and an alkoxysilane group in a molecule, and the azo group exhibits high reactivity with a double bond in the polymer main chain. As a side chain, a functional group derived from a denaturant may be introduced into the polymer main chain, and thus a functional group derived from a denaturant may be introduced into the terminal and side chains to denature the polymer with a high denaturation rate, and the ester group increases the affinity for the polymerization solvent to increase the affinity for the denaturant. To increase the solubility of the can be made to facilitate the denaturation reaction to improve the denaturation rate, the alkoxysilane group can prevent the aggregation between the fillers in the rubber composition can improve the dispersibility of the filler. As an example, when silica, which is a type of inorganic filler, is used as a filler, aggregation is likely to occur due to hydrogen bonding between hydroxyl groups present on the surface of the silica. The alkoxysilane group interferes with hydrogen bonding between the hydroxyl groups of silica to improve the dispersibility of silica. Can be improved. In addition, the ester group can improve the stability of the modifier by reducing the electron density of the azo group.

As described above, the denaturing agent has a structure capable of maximizing the compounding properties of the modified conjugated diene-based polymer, and thus can efficiently manufacture a modified conjugated diene-based polymer having excellent balance of mechanical properties such as wear resistance and processability of the rubber composition.

On the other hand, in the modified conjugated diene-based polymer according to an embodiment of the present invention, the polymer may be one containing a functional group derived from a modifier in the side chain. That is, the functional group derived from the denaturant may be a side chain bound to the main chain constituting the polymer, and a specific example may have a structure represented by the following Chemical Formula 2.

[Formula 2]

In Chemical Formula 2, R ₁ to R ₅ are as defined in Chemical Formula 1, and a and b represent the proportion of units constituting the polymer, and a+b may be 100 mol%.

Specifically, the modifier represented by Chemical Formula 1 according to an embodiment of the present invention includes an azo group, a double bond in a polymer, that is, a double bond in a main chain composed of a unit derived from a conjugated diene-based monomer and the above An azo group reacts, and as a side chain of the main chain, a functional group derived from a modifier may be combined to denature the conjugated diene-based polymer.

In addition, the polymer according to an embodiment of the present invention may include a functional group derived from a modifier represented by Chemical Formula 1 at least at one end.

That is, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a structure containing a modifier-derived functional group in a side chain, and in addition, at least one terminal also includes a modifier-derived functional group.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a denaturation rate of 5 mol% to 80 mol%, and specifically, may have a denaturation rate of 10 mol% to 60 mol%.

Here, the modification rate (modification rate) represents the ratio of the conjugated diene-based monomer derived unit having a functional group derived from the modifier represented by Formula 1 in the modified conjugated diene-based polymer, that is, the ratio of b in Formula 2 It may be.

Meanwhile, in one embodiment of the present invention, the denaturation rate was calculated using a chromatogram obtained from chromatographic measurement. Specifically, the polymer is dissolved in tetrahydrofuran (THF) under a condition of 40°C to prepare a sample, the sample is injected into gel permeation chromatography (GPC), and tetrahydrofuran is flowed with an eluent. A given chromatogram was obtained, and the denaturation rate was calculated by the following equation (1) from the obtained chromatogram.

[Equation 1]

Denaturation rate (%) = [(Peak area derived from conjugated diene-based monomer to which functional group derived from a modifier is bound)/(total peak area of modified conjugated diene-based polymer)] X 100

Further, the modified conjugated diene-based polymer may be a butadiene homopolymer such as polybutadiene, or a diene-based copolymer such as a butadiene-isoprene copolymer.

As a specific example, the modified conjugated diene-based polymer may include 80 to 100% by weight of a unit derived from 1,3-butadiene monomer, and optionally 20% by weight or less of a unit derived from other conjugated diene-based monomer copolymerizable with 1,3-butadiene. It can be, there is an effect that does not decrease the 1,4-cis bond content in the polymer within the above range. At this time, the 1,3-butadiene monomers include 1,3-butadiene or derivatives thereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene. Other conjugated diene-based monomers that can be copolymerized with 1,3-butadiene include 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, and 4 -Methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, and the like, and any one or more of these compounds may be used.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a neodymium catalyzed modified conjugated diene-based polymer. That is, the modified conjugated diene-based polymer may be a conjugated diene-based polymer including an organometallic site activated from a catalyst composition containing a neodymium compound.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) at 100°C of 20 or more and 100 or less, specifically 30 or more and 80 or less, 35 or more and 75 or less Or 40 or more and 70 or less. The modified conjugated diene-based polymer according to the present invention may have excellent processability by having a Mooney viscosity in the above-described range.

In the present invention, the Mooney viscosity was measured under conditions of 100° C. and Rotor Speed 2±0.02 rpm using a Mooney viscometer, for example, a large rotor of MV2000E from Monsanto. Specifically, after the polymer was left at room temperature (23±5°C) for 30 minutes or more, 27±3 g was collected, filled into the die cavity, and a platen was operated to apply a torque while measuring the Mooney viscosity.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 2.0 to 3.5, and more specifically, may have a molecular weight distribution of 2.5 to 3.5, 2.5 to 3.2 or 2.6 to 3.0.

In the present invention, the molecular weight distribution of the modified conjugated diene-based polymer can be calculated from the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn). In this case, the number average molecular weight (Mn) is a common average of the individual polymer molecular weights calculated by dividing n by measuring the molecular weight of n polymer molecules and obtaining the sum of these molecular weights, and the weight average molecular weight (Mw) is the polymer The molecular weight distribution of the composition is shown. All molecular weight averages can be expressed in grams per mole (g/mol). In addition, the weight-average molecular weight and the number-average molecular weight may mean molecular weights in terms of polystyrene, which are respectively analyzed by gel permeation chromatography (GPC).

The modified conjugated diene-based polymer according to an embodiment of the present invention may satisfy the above molecular weight distribution conditions, and the weight average molecular weight (Mw) may be 3 X 10 ⁵ to 1.5 X 10 ⁶ g/mol, and the number average Molecular weight (Mn) may be from 1.0 X 10 ⁵ to 5.0 X 10 ⁵ g/mol, excellent in tensile properties when applied to a rubber composition within this range, and excellent in processability, resulting in improved kneading due to improved workability of the rubber composition Easy, there is an excellent effect of mechanical properties and physical properties balance of the rubber composition. The weight average molecular weight may be, for example, 5 X 10 ⁵ to 1.2 X 10 ⁶ g/mol, or 5 X 10 ⁵ to 8 X 10 ⁵ g/mol, and the number average molecular weight may be, for example, 1.5 X 10 ⁵ to 3.5 X. 10 ⁵ g/mol, or 2.0 X 10 ⁵ to 2.7 X 10 ⁵ g/mol.

More specifically, when the modified conjugated diene-based polymer according to an embodiment of the present invention simultaneously meets the weight average molecular weight (Mw) and number average molecular weight conditions together with the above-described molecular weight distribution, the rubber composition is applied to the rubber composition. It has excellent tensile properties, viscoelasticity and workability, and excellent physical property balance between them.

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

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

Here, the cis-1,4 binding 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 using carbon disulfide in the same cell as a blank. After measuring the FT-IR transmittance spectrum of the carbon disulfide solution of, the maximum peak value (a, baseline) around 1130 cm ^-1 of the measurement spectrum, the minimum peak around 967 cm ^-1 indicating the trans-1,4 binding Using the value (b), the minimum peak value (c) near 911 cm ^-1 indicating vinyl bonding, and the minimum peak value (d) near 736 cm ^-1 indicating cis-1,4 bonding, respectively I got it.

In addition, the present invention provides a method for preparing the modified conjugated diene-based polymer.

The production method according to an embodiment of the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent (step 1); And reacting the active polymer with a modifier represented by the following Chemical Formula 1 (step 2).

[Formula 1]

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

Step 1 is a step of polymerizing the conjugated diene-based monomer to prepare an active polymer including an organometallic moiety, and may be performed by polymerizing the conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent.

In the present invention, the organometallic moiety in the active polymer comprising the organometallic moiety is an activated organometallic moiety at the end of the conjugated diene-based polymer (activated organometallic moiety at the molecular chain end), an active organometallic in the main chain. It may be a site or an activated organometallic site in a side chain (side chain), among which, when an activated organometallic part of the conjugated diene-based polymer is obtained by anionic polymerization or coordination anionic polymerization, the organometallic site is a terminal activated organometallic. It may indicate a site.

The conjugated diene monomer is not particularly limited, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl Group consisting of -1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene and 2,4-hexadiene It may be one or more selected from.

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, cyclohexane, toluene, benzene and xylene.

The catalyst composition may be used in an amount such that the neodymium compound is 0.1 mmol to 0.5 mmol based on 100 g of the conjugated diene-based monomer, specifically, the neodymium compound is based on the total of 100 g of the conjugated diene-based monomer. 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.

The neodymium compound is a carboxylate thereof (for example, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium sulphate, neodymium maleate, neodymium oxalate, neodymium 2 -Ethyl hexanoate, neodymium neo decanoate, etc.); Organophosphates (e.g. neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis (1-methyl heptyl) phosphate, neodymium bis (2-ethylhexyl) Phosphate, or neodymium didecyl phosphate, etc.); Organic phosphonates (e.g. neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, Neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate, etc.); Organic phosphinates (e.g. neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methyl heptyl) phosphinate or Neodymium (2-ethylhexyl) phosphinate, etc.); Carbamate (eg, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate); Dithio carbamate (eg, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithio carbamate or neodymium dibutyldithiocarbamate); Xanthogenates (eg, neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl xanthogenate, or neodymium benzyl xanthogenate); 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); Halides or pseudohalides (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 neodymium-containing compound containing at least one neodymium element-carbon bond (e.g., Cp ₃ Nd, Cp ₂ NdR, Cp ₂ NdCl, CpNdCl ₂ , CpNd (cyclooctatetraene), (C ₅ Me ₅ ) ₂ And NdR, NdR ₃ , Nd(allyl) ₃ , or Nd(allyl) ₂ Cl, wherein R is a hydrocarbyl group), and the like, and may include any one or a mixture of two or more.

The neodymium compound may be a compound represented by Formula 3 below.

[Formula 3]

In the formula (3), R _a to R _c are each 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.

More specifically, the neodymium compound is Nd(2-ethylhexanoate) ₃ , Nd(2,2-dimethyl decanoate) ₃ , Nd(2,2-diethyl decanoate) ₃ , Nd(2, 2-dipropyl decanoate) ₃ , Nd(2,2-dibutyl decanoate) ₃ , Nd(2,2-dihexyl decanoate) ₃ , Nd(2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl decanoate) ₃ , Nd (2-ethyl-2-butyl decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2 -Propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-isopropyl decanoate) ₃ , Nd(2-butyl-2 -Hexyl decanoate) ₃ , Nd(2-hexyl-2-octyl decanoate) ₃ , Nd(2,2-diethyl octanoate) ₃ , Nd(2,2-dipropyl octanoate) ₃ , Nd(2,2-dibutyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl- 2-hexyl octanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd(2,2-dipropyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) ₃ , Nd (2,2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ 1 selected from the group consisting of It may be more than a species.

In addition, in another example, considering the excellent solubility in a solvent without concern about oligomerization, the conversion rate to catalytically active species, and thus the effect of improving catalytic activity, the neodymium compound is more specifically R _a in Formula 3 It is an alkyl group having 4 to 12 carbon atoms, and R _b and R _c are each independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R _b and R _c are not hydrogen at the same time.

More specifically, in Formula 3, R _a is an alkyl group having 6 to 8 carbon atoms, 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 are At the same time, it may not be hydrogen, and specific examples thereof include Nd(2,2-diethyl decanoate) ₃ , Nd(2,2-dipropyl decanoate) ₃ , and Nd(2,2-dibutyl decanoate) ) ₃ , Nd(2,2-dihexyl decanoate) ₃ , Nd(2,2-dioctyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2- Ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl Decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd(2-t-butyl decanoate) ₃ , Nd(2,2-diethyl octanoate) ₃ , Nd(2,2-dipropyl octanoate) ₃ , Nd(2,2-di Butyl 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-di Hexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) _{3 It} may be one or more selected from the group consisting of, among them 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 , and Nd(2,2-dioctyl decanoate) ₃ .

More specifically, in Chemical Formula 3, R _a is an alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be an alkyl group having 2 to 6 carbon atoms.

As described above, the neodymium-based compound represented by Chemical Formula 3 includes a carboxylate ligand including an alkyl group having various lengths of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a dimensional change around the neodymium center metal. It is possible to block the entanglement of the liver, and accordingly, there is an effect of suppressing oligomerization. In addition, such a neodymium-based compound has a high solubility in a solvent, and the ratio of neodymium located in a central portion having difficulty in converting to a catalytically active species is reduced, resulting in high conversion to a catalytically active species.

In addition, the solubility of the neodymium compound according to an embodiment of the present invention may be about 4 g or more per 6 g of a non-polar solvent at room temperature (25° C.).

In the present invention, the solubility of the neodymium-based compound means a degree of clear dissolution without turbidity, and thus can exhibit excellent catalytic activity by exhibiting such high solubility.

In addition, the neodymium 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 an effect of improving the solubility of the neodymium compound in a solvent by a Lewis base and storing it in a stable state for a long time. The Lewis base may be used, for example, in a proportion of 30 mol or less per 1 mol of neodymium, or 1 to 10 mol. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organophosphorus compound, monovalent or divalent alcohol, or the like.

Meanwhile, the catalyst composition may further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer together with a neodymium compound.

That is, the catalyst composition according to an embodiment of the present invention includes a neodymium compound, and may further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer.

Hereinafter, the (a) alkylating agent, (b) halide and (c) conjugated diene-based monomer will be described in detail.

(a) Alkylating agent

The alkylating agent may be an organometallic compound capable of transferring a hydrocarbyl group to another metal, and may serve as a cocatalyst. The alkylating agent can be used without particular limitation as long as it is usually used as an alkylating agent in the production of a diene-based polymer. For example, it is soluble in a polymerization solvent, such as an organic aluminum compound, an organic magnesium compound, or an organic lithium compound, and has a metal-carbon bond. It may be an organometallic compound.

Specifically, the organic aluminum compound includes trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl Alkyl aluminum such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; Diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride (DIBAH), di-n-octyl aluminum hydride, Diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenyl isopropyl aluminum hydride, phenyl-n-butyl aluminum hydride Ride, phenyl isobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, p-tolyl- n-butyl aluminum hydride, p-tolyl isobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl dihydrocarbyl aluminum hydride such as -n-butyl aluminum hydride, benzyl isobutyl aluminum hydride or benzyl-n-octyl aluminum hydride; Hydrocarbyl aluminum dihydride such as ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride or n-octyl aluminum dihydride. And hydrides. Examples of the organic magnesium compound include diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, or alkylmagnesium compounds such as dibenzylmagnesium. Examples of the organic lithium compound include alkyl lithium compounds such as n-butyl lithium.

In addition, the organoaluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting a trihydrocarbyl aluminum-based compound with water, and may be specifically, a straight-chain aluminoxane of Formula 4a or a cyclic aluminoxane of Formula 4b.

[Formula 4a]

[Formula 4b]

In the formulas 4a and 4b, R is a monovalent organic group that is attached 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 or the like, and any one or a mixture of two or more of them may be used.

In addition, the modified methylaluminoxane is a methyl group of methylaluminoxane substituted with a modifier (R), specifically a hydrocarbon group having 2 to 20 carbon atoms, and may be specifically a compound represented by the following formula (5).

[Formula 5]

In Chemical Formula 5, R is as defined above, and m and n may be an integer of 2 or more independently of each other. In addition, in Chemical Formula 5, Me represents a methyl group.

Specifically, in Formula 5, 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, 2 carbon atoms such as an ethyl group, an isobutyl group, a hexyl group, or an octyl group. To 10 alkyl groups, and more specifically, may be an isobutyl group.

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

Such modified methyl aluminoxane may be prepared according to a conventional method, and specifically, may be prepared using trimethyl aluminum and alkyl aluminum other than trimethyl aluminum. At this time, the alkyl aluminum may be triisobutyl aluminum, triethyl aluminum, trihexyl aluminum or trioctyl aluminum, and any one or a mixture of two or more of them may be used.

In addition, the catalyst composition according to an embodiment of the present invention may include the alkylating agent in a 1 to 200 molar ratio, specifically 1 to 100 molar ratio, more specifically 3 to 20 molar ratio to 1 mole of the neodymium compound. have. If the alkylating agent contains more than 200 molar ratio, it is not easy to control the catalytic reaction when preparing the polymer, and there is a fear that an excessive alkylating agent may cause a side reaction.

(b) halide

The halide is not particularly limited, and examples thereof include a halogen simple substance, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometal halide. One or two or more mixtures may be used. Considering the superiority of the catalytic activity improvement and thus the reactivity improvement effect, any one or two or more mixtures selected from the group consisting of organic halides, metal halides and organometal halides may be used.

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

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

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

In addition, the organic halide includes 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 Oenyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called'iodoform'), tetraiodomethane, 1-iodo Dopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called'neopentyl iodide'), allyl yo Odide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called'benzal iodide'), trimethylsilyl iodide, triethyl Silyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, And benzoyl iodide, propionyl iodide, or methyl iodoformate.

In addition, the non-metal halide includes 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 tetraiodide, Arsenic triiodide, Arsenic iodide, Tellurium tetraiodide, Boron triiodeide, Phosphorus triiodide, Phosphorus iodinide Can be heard.

Further, the metal halide includes 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 triiodide, gallium iodide, indium triiodide, indium iodide, titanium iodide, zinc iodide And germanium, tin iodide, tin iodide, antimony triiodide, or magnesium iodide.

In addition, the organometal halide is dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum di Bromide, ethyl aluminum dibromide, methyl aluminum difluoride, ethyl aluminum difluoride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride (EASC), isobutyl aluminum sesquichloride, methyl magnesium chloride, methyl magnesium bromide, ethyl Magnesium chloride, 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 , Methyl magnesium iodide, dimethyl aluminum iodide, diethyl aluminum iodide, di-n-butyl aluminum iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum Diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, methyl aluminum sesquiiodide, ethyl aluminum sesquiiodide, isobutyl aluminum sesquiiodide, ethyl magnesium yo Odide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin Odide, di-n-butyl tin diiodide, or di-t-butyl tin diiodide.

In addition, the catalyst composition according to an embodiment of the present invention is 1 mole to 20 moles, more specifically 1 mole to 5 moles, and more specifically 2 moles to 3 moles of the halide to 1 mole of the neodymium compound. It can contain. If the halide is contained in an amount exceeding 20 molar ratio, the removal of the catalytic reaction is not easy, and an excessive amount of halide may cause a side reaction.

In addition, the catalyst composition 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 sterically bulky anion that does not form a coordination bond with the active center of the catalyst system due to steric hindrance, tetraarylborate anion or tetraaryl fluoride And borate anions. In addition, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation together with the non-coordinating anion; It may be an ammonium cation such as an N,N-dialkyl anilium cation, or a counter cation such as a phosphonium cation. More specifically, the compound containing the non-coordinating anion may include triphenyl carbonate tetrakis (pentafluoro phenyl) borate, N,N-dimethylanilinium tetrakis (pentafluoro phenyl) borate, and triphenyl carbonate tetra. Keith[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, a compound capable of forming a non-coordinating anion under reaction conditions, a triaryl boron compound (BE ₃ , where E is a pentafluorophenyl group or a 3,5-bis(trifluoromethyl) phenyl group, etc.) And the same strong electron-withdrawing aryl group).

(c) conjugated diene monomer

In addition, the catalyst composition may further include a conjugated diene-based monomer, and pre-polymerization or pre-polymerization of a part of the conjugated diene-based monomer used in the polymerization reaction with a catalyst composition for polymerization in advance. By using it in the form of a premix catalyst composition, it is possible to not only improve the catalyst composition activity, but also stabilize the prepared active polymer.

In the present invention, the term "preforming" means a catalyst composition comprising a neodymium compound, an alkylating agent, and a halide, that is, when diisobutylaluminum hydride (DIBAH) or the like is included in the catalyst system, the various In order to reduce the possibility of generating active species of the catalyst composition, a small amount of a conjugated diene-based monomer such as 1,3-butadiene is added, and it may mean that pre-polymerization is performed in the catalyst composition system together with the addition of 1,3-butadiene. have. Also, "premix" may mean a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

At this time, the conjugated diene-based monomer used in the preparation of the catalyst composition may be a portion of the total amount of the conjugated diene-based monomer used in the polymerization reaction may be used, for example, 1 to 1 mole of the neodymium compound Molar to 100 moles, specifically 10 to 50 moles, or 20 to 50 moles may be used.

The catalyst composition according to an embodiment of the present invention is at least one of the above-mentioned neodymium compounds and alkylating agents, halides and conjugated diene-based monomers in an organic solvent, specifically neodymium compounds, alkylating agents and halides, and optionally conjugated diene It can be prepared by mixing the system monomers. At this time, the organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition. Specifically, the non-polar 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; A mixed solvent of an aliphatic hydrocarbon having 5 to 20 carbon atoms, such as petroleum ether or petroleum spirits, or kerosene; Or it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, xylene, or the like, and any one or a mixture of two or more of them may be used. More specifically, the non-polar solvent may be a linear, branched or cyclic aliphatic hydrocarbon or a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, and more specifically, n-hexane, cyclohexane, or a mixture thereof. Can.

In addition, the organic solvent may be appropriately selected depending on the constituent components constituting the catalyst composition, particularly the type of alkylating agent.

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

In addition, when a modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon-based solvent can be suitably used. In this case, since a single solvent system can be implemented together with an aliphatic hydrocarbon-based 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-based solvent can promote catalytic activity, and reactivity can be further improved by the catalytic activity.

Meanwhile, the organic solvent may be 20 mol to 20,000 mol with respect to 1 mol of the neodymium compound, and more specifically, 100 mol to 1,000 mol.

Meanwhile, the polymerization of step 1 may be performed by continuous polymerization in a polymerization reactor including at least two reactors, or may be performed in a batch reactor.

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

Here, the constant temperature polymerization refers to a polymerization method comprising the step of polymerizing with the reaction heat itself without adding any heat after the introduction of the catalyst composition, and the elevated temperature polymerization is a polymerization method of increasing the temperature by optionally adding heat after the introduction of the catalyst composition The isothermal polymerization refers to a polymerization method in which the temperature of the reactants is kept constant by increasing heat or taking heat by adding heat after the introduction of the catalyst composition.

In addition, the polymerization may be performed using coordination anionic polymerization, or may be performed by radical polymerization, specifically bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and more specifically solution polymerization. .

The polymerization may be performed in a temperature range of -20°C to 200°C, specifically 50°C to 150°C, more specifically 15 minutes to a temperature range of 10°C to 120°C or 60°C to 90°C It may be performed for 3 hours. If, when the polymerization temperature exceeds 200 ℃, it is difficult to sufficiently control the polymerization reaction, there is a fear that the cis-1,4 bond content of the resulting conjugated diene polymer is lowered, and if the temperature is less than -20 ℃ polymerization There is a fear that the reaction rate and efficiency are lowered.

In addition, the method for preparing the modified conjugated diene-based polymer according to an embodiment of the present invention is a reaction stopper for completing a polymerization reaction such as polyoxyethylene glycol phosphate after preparing the active polymer; Or it may include the step of terminating the polymerization by using an additive such as an antioxidant such as 2,6-di-t-butylparacresol. In addition, additives that facilitate solution polymerization together with a reaction stopper, such as a chelating agent, a dispersing agent, a pH adjusting agent, an oxygen scavenger, or an oxygen scavenger, may be optionally used.

Step 2 is a step of preparing a modified conjugated diene-based polymer including a functional group by modifying or coupling an active polymer, and may be performed by reacting the active polymer with a modifier represented by Chemical Formula 1.

Typically, in the case of reacting the active polymer with the modifier, as described above, the organometallic moiety is present at the end of the active polymer, so that the reaction between the polymer end and the modifier occurs, and thus the modified polymer having a structure in which the modifier-derived functional group is bonded to the end of the polymer Only can be manufactured.

However, in the production method according to an embodiment of the present invention, the reaction of the double bond in the polymer chain composed of the unit derived from the conjugated diene-based monomer and the azo group in the denaturant as shown in Reaction Scheme 1 below by using the denaturant represented by Formula 1 This occurs, and the polymer side chain may also have a functional group derived from a denaturant.

[Scheme 1]

In Reaction Scheme 1, 1 is a polymer main chain composed of a unit derived from a conjugated diene-based monomer, 2 is a modifier, and 3 is a structure of a polymer having a functional group derived from a modifier.

Accordingly, the modified conjugated diene-based polymer prepared through the above-described manufacturing method according to an embodiment of the present invention may include a modifier-derived functional group in the polymer side chain, and at least one terminal may include a modifier-derived functional group.

The denaturing agent may be used in 0.5 mol to 20 mol compared to 1 mol of the neodymium compound in the catalyst composition. Specifically, the denaturing agent may be used in a mole ratio of 1 to 15 moles compared to 1 mole of the neodymium compound in the catalyst composition, and more specifically, 2 mole to 15 moles compared to 1 mole of the neodymium compound in the catalyst composition.

In addition, the denaturation reaction may be to perform the reaction for 1 minute to 5 hours at 0 ℃ to 90 ℃.

After completion of the above-described denaturation reaction, a polymerization reaction can be stopped by adding an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) to the polymerization reaction system.

The production method according to an embodiment of the present invention can obtain a modified conjugated diene-based polymer through desolvation treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through the supply of water vapor after step 2. . In addition, an unmodified, active polymer may be included in the reaction product obtained as a result of the above-described reaction together with the above-mentioned modified conjugated diene polymer.

Furthermore, the present invention provides a rubber composition comprising the 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 a modified conjugated diene-based polymer of 0.1% by weight or more and 100% by weight or less, specifically 10% by weight to 100% by weight, more specifically 20% by weight to 90% by weight It may be included. If, if the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, a molded article manufactured using the rubber composition, for example, the improvement effect of wear resistance and crack resistance of the tire may be insignificant.

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

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, which have been modified or purified from 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, synthetic rubber such as halogenated butyl rubber, etc., any one or a mixture of two or more of them may be used.

Further, the rubber composition may include 0.1 parts by weight to 150 parts by weight of a filler relative to 100 parts by weight of the modified conjugated diene-based polymer, and the filler may be silica-based, carbon black, or a combination thereof. Specifically, the filler may be carbon black.

The carbon black-based filler is not particularly limited, but may have, for example, a nitrogen adsorption specific surface area (measured according to N ₂ SA, JIS K 6217-2:2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutylphthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. When the nitrogen black specific surface area of the carbon black exceeds 250 m ² /g, the workability of the rubber composition may be deteriorated, and if it is less than 20 m ² /g, the reinforcement performance by the carbon black may be insignificant. In addition, when the DBP oil absorption amount of the carbon black exceeds 200 cc/100 g, the workability of the rubber composition may be deteriorated, and if it 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 (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica may be wet silica having the most remarkable effect of improving the fracture properties and the compatibility of wet grip. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen surface area per gram, N ₂ SA) of 120 m 2 /g to 180 m 2 /g, and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 m 2 /g to 200 m 2 /g. If the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, there is a fear that the reinforcing performance by the silica is lowered, and when it exceeds 180 m 2 /g, the workability of the rubber composition may be lowered. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, there is a fear that the reinforcing performance by the silica, which is a filler, may decrease, and if it exceeds 200 m 2 /g, the workability of the rubber composition may decrease.

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

Specifically, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis (2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasul Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl Tetrasulfide and the like, and any one or a mixture of two or more of them may be used. More specifically, when considering the effect of improving the reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

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 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time, low fuel efficiency can be obtained.

In addition, the rubber composition according to an embodiment of the present invention, in addition to the above-mentioned components, various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, anti-aging agents, scorch inhibitors, zinc white ), stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is not particularly limited, specifically M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. A thiazole-based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in 0.1 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 paraffin-based, naphthenic-based, or aromatic-based compound, and more specifically, considering the tensile strength and abrasion resistance, the aromatic-based process oil, hysteresis loss And when considering low-temperature properties, naphthenic or paraffinic process oils may be used. 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, and when included in the content, the tensile strength of the vulcanized rubber, low heat generation (low fuel consumption) can be prevented from falling.

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

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

Accordingly, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreatic, or bead coated rubber, each member of a tire, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture 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 by examples and experimental examples. However, the following examples and experimental examples are intended to illustrate the present invention, but the scope of the present invention is not limited to them.

Preparation Example 1

In an ice bath, add 15 g of 3-(triethoxysilyl)propyl isocyanate to a 100 ml round-bottom flask, add acetonitrile, and slowly add 6.3 g of ethyl carbazate dropwise. To react. Thereafter, a solvent was removed using a rotary evaporator to obtain a white solid.

The white solid was added to a 100 ml round-bottom flask, dichloromethane (CH ₂ Cl ₂ ) and 9.7 ml of pyridine were sequentially added, and 10.8 g of N-bromosuccinimide was slowly added dropwise in an ice bath. Then, the solvent was removed using a rotary evaporator, dissolved in dichloromethane, and extracted with water to obtain a red liquid, from which a denaturant represented by Chemical Formula 1-1 was obtained (yield 96%). ^{The 1} H nuclear magnetic resonance spectroscopy spectrum was observed to confirm the denaturant represented by the following Chemical Formula 1-1.

[Formula 1-1]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 9.09 (1H, t), 4.46 (2H, q), 3.75 (6H, q), 3.23 (2H, d), 1.58 (2H, t), 1.34 ( 3H, t), 1.14 (9H, t), 0.61 (2H, t).

Preparation Example 2

In an ice bath, add 100 g of hydrazine monohydrate to a 100 ml round-bottom flask, add 125 ml of acetonitrile, and slowly 98 ml of 2-ethylhexyl chloroformate. It reacted while dropping. Thereafter, the solvent was removed using a rotary evaporator, and then dissolved by adding dimethyl ether, followed by extraction with NaHCO ₃ aqueous solution and separation to obtain a pink solution.

3.8 g of 3-(triethoxysilyl)propyl isocytate was added to a 100 ml round-bottom flask, acetonitrile was added, and 4.3 g of the pink solution was slowly added dropwise to react. Thereafter, a solvent was removed using a rotary evaporator to obtain a white solid.

In a 100 ml round-bottom flask, 6.7 g of the white solid was added, and dichloromethane (CH ₂ Cl ₂ ) and pyridine 1.8 ml were sequentially added to dissolve the solid and reacted slowly while dropping 2.7 g of N-bromosuccinimide in an ice bath. Ordered. Thereafter, the solvent was removed using a rotary evaporator, dissolved in dichloromethane, and extracted with water to obtain a red color denaturer represented by Chemical Formula 1-2 (yield 80%). ¹ H nuclear magnetic resonance spectroscopy spectrum was observed to confirm the denaturant of Formula 1-2 below.

[Formula 1-2]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 9.1 (1H, d), 4.36 (2H, m), 3.75 (6H, q), 3.22 (2H, d), 1.69 (1H, m), 1.58( 2H, m), 1.14 (9H, t), 0.88 (6H, m), 0.56 (2H, m).

Example 1

After adding 900 g of 1,3-butadiene and 6,600 g of n-hexane to a 20 L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added thereto, polymerization was performed for 60 minutes. In this case, the catalyst composition is added to a neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay) in n-hexane solvent, diisobutyl aluminum hydride (DIBAH), diethyl aluminum Chloride (DEAC) was prepared by sequentially adding to the molar ratio of neodymium versate:DIBAH:DEAC=1:16:2.4, followed by mixing. After adding the modifier of Formula 1-1 prepared in Preparation Example 1, a denaturation reaction was performed at 70° C. for 30 minutes (denaturant:Nd=1:1 molar ratio). Thereafter, the reaction was terminated by adding a solution in which 30 wt% of hexane solution containing 1.0 g of polymerization stopper and antioxidant WINGSTAY (Eliokem SAS, France) were dissolved in hexane, and the resulting heavy product was heated with steam. After stirring in hot water to remove the solvent, the roll was dried to remove the residual amount of solvent and water to prepare a modified butadiene polymer.

Example 2

In Example 1, the modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier of Chemical Formula 1-1 was added at a 2:1 molar ratio (modifier:Nd=2:1 molar ratio) to neodymium in the catalyst composition. It was prepared.

Example 3

In Example 1, the modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier of Chemical Formula 1-1 was added in a 15:1 molar ratio (neutral modifier:Nd=15:1 molar ratio) to neodymium in the catalyst composition. It was prepared.

Example 4

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier of Formula 1-2 prepared in Preparation Example 2 was used instead of the modifier of Formula 1-1.

Comparative Example 1

As an unmodified butadiene polymer, CB25 (Lanxess Co.) was used as a comparative example.

Comparative Example 2

After adding 900 g of 1,3-butadiene and 6,600 g of n-hexane to a 20 L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added thereto, polymerization was performed for 60 minutes. In this case, the catalyst composition is added to a neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay) in n-hexane solvent, diisobutyl aluminum hydride (DIBAH), diethyl aluminum Chloride (DEAC) was prepared by sequentially adding to the molar ratio of neodymium versate:DIBAH:DEAC=1:16:2.4, followed by mixing. Thereafter, the reaction was terminated by adding a solution in which 30 wt% of hexane solution containing 1.0 g of polymerization stopper and antioxidant WINGSTAY (Eliokem SAS, France) were dissolved in hexane, and the resulting heavy product was heated with steam. After stirring in hot water to remove the solvent, the roll was dried to remove the residual amount of solvent and water to prepare an unmodified butadiene polymer.

Experimental Example 1

The properties of the polymers of Examples 1 to 4 and Comparative Examples 1 and 2 were measured in the following manner, and the results are shown in Table 1 below.

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

Each polymer was dissolved in tetrahydrofuran (THF) for 30 minutes under a condition of 40° C., and then loaded and flowed through gel permeation chromatography (GPC). At this time, the column was used in combination of two PLgel Olexis column and one PLgel mixed-C column of the polymer Laboratories (Polymer Laboratories). In addition, all newly replaced columns used a mixed bed type column, and polystyrene was used as a gel permeation chromatography standard material.

2) Mooney viscosity (RP, Raw polymer)

For each polymer, Mooney viscosity (ML1+4, @100°C) (MU) was measured at 100°C under conditions of Rotor Speed 2±0.02 rpm using a large rotor with MV2000E from Monsanto. At this time, the sample used was left at room temperature (23±3°C) for 30 minutes or more, and then 27±3 g was collected, filled inside the die cavity, and a platen was operated to apply a torque to measure the Mooney viscosity.

3) Denaturation rate

The denaturation rate was calculated using a chromatogram obtained from chromatographic measurements. Specifically, each polymer is dissolved in tetrahydrofuran (THF) under 40°C to prepare a sample, and the sample is injected into gel permeation chromatography (GPC), and tetrahydrofuran is used as an eluent. The flow rate was obtained to obtain a chromatogram, and the denaturation rate was calculated by the following equation (1) from the obtained chromatogram.

[Equation 1]

Denaturation rate (%) = [(Peak area derived from conjugated diene-based monomer to which functional group derived from a modifier is bound)/(All peak area of modified conjugated diene-based polymer)] × 100

division Example Comparative example One 2 3 4 One 2 GPC results Mn (x10 ⁵ g/mol) 1.93 2.07 2.11 2.05 2.64 2.13 Mw (x10 ⁵ g/mol) 4.73 4.84 4.90 4.80 6.18 4.92 MWD (Mw/Mn) 2.45 2.34 2.32 2.34 2.35 2.31 Mooney viscosity (RP) (ML1+4, @100℃) (MU) 47.0 50.0 48.0 48.0 46.0 46.0 Denaturation rate (%) 32 55 60 58 0 0

As shown in Table 1, it was confirmed that the polymers of Examples 1 to 4 according to an embodiment of the present invention had a denaturation rate of 30 to 60%, through which it was found that the functional group derived from the modifier in the polymer was included. Can.

Experimental Example 2

After preparing the rubber composition and the rubber specimen using the polymers of Examples 1 to 4 and Comparative Examples 1 and 2, the Mooney viscosity, tensile stress, 300% modulus, abrasion resistance, and viscoelastic properties, respectively, were as follows. It was measured. The results are shown in Table 2 below.

First, the rubber composition and the rubber specimen were prepared as follows.

1) Preparation of rubber composition and rubber specimen

① Example 1 to Example 4, Comparative Example 1 and Comparative Example 2

In Examples 1 to 4, 100 parts by weight of each polymer of Comparative Examples 1 and 2, 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of anti-aging agent (TMDQ), zinc oxide (ZnO) 3 parts by weight and stearic acid (stearic acid) 2 parts by weight of each rubber composition was prepared. Thereafter, 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 rubber composition, and the mixture was gently mixed at 50 rpm for 50 minutes at 50°C, and then a roll of 50°C was used. Thus, a vulcanized compound in a sheet form was obtained. The obtained vulcanized formulation was vulcanized at 160°C for 25 minutes to prepare a rubber specimen.

② Comparative Example 3

100 parts by weight of the polymer of Comparative Example 1, the modifier of Chemical Formula 1-1 prepared in Preparation Example 1, 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of anti-aging agent (TMDQ), zinc oxide ( ZnO) 3 parts by weight and stearic acid (2 parts by weight) were combined to prepare respective rubber compositions. Thereafter, 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 rubber composition, and the mixture was gently mixed at 50 rpm for 50 minutes at 50°C, and then a roll of 50°C was used. Thus, a vulcanized compound in a sheet form was obtained. The obtained vulcanized formulation was vulcanized at 160°C for 25 minutes to prepare a rubber specimen. Here, the modifier was used in 2 equivalents to 1 equivalent of the polymer.

③ Comparative Example 4

In Comparative Example 3, a rubber composition and a rubber specimen were prepared in the same manner as in Comparative Example 3, except that the modifier was used in an amount of 20 equivalents to 1 equivalent of polymer.

④ Comparative Example 5

In Comparative Example 3, a rubber composition and a rubber specimen were prepared in the same manner as in Comparative Example 3, except that the polymer of Comparative Example 2 was used instead of the polymer of Comparative Example 1.

2) Mooney viscosity (FMB, Final Master Batch) and Mooney viscosity difference (△MV)

Mooney viscosity (ML1+4, @100°C) (MU) was measured using each vulcanized formulation prepared above. Specifically, the Mooney viscosity (MV) was measured under the condition of Rotor Speed 2±0.02 rpm at 100°C using a large rotor with Monsanto MV2000E. At this time, the sample used was left at room temperature (23±3℃) for more than 30 minutes, and then 27±3g was collected, filled inside the die cavity, and operated by a platen to measure the Mooney viscosity (FMB) while applying torque. Did.

In addition, the difference between the Mooney viscosity of each polymer shown in Table 1 and the Mooney viscosity of the formulation (ΔMV, FMB-RP) was calculated, and the smaller the Mooney viscosity difference, the better the processability. Meanwhile, the polymer Mooney viscosity of Comparative Example 3 and Comparative Example 4 is the same as that of Comparative Example 1, and the polymer Mooney viscosity of Comparative Example 5 is the same as that of Comparative Example 2.

3) Tensile stress and 300% modulus

After curing each rubber composition at 150° C. for t90 minutes, tensile stress and modulus at 300% elongation (M-300%) were measured according to ASTM D412.

4) Wear resistance (DIN wear test)

Each rubber specimen was subjected to a DIN wear test in accordance with ASTM D5963, and represented by DIN wt loss index (loss volume index: ARIA (Abrasion resistance index, Method A)).

5) Viscoelastic properties

The most important Tan δ property for low fuel efficiency was the viscoelastic modulus (Tan δ) at -60°C to 60°C at 10 kHz, 3% Prestrain and 3% Dynamic Strain using DMTS 500N from Gabo, Germany. At this time, the Tanδ value at 0°C indicates a low road surface resistance, and the Tanδ value at 60°C indicates a rotational resistance characteristic (fuel efficiency).

division Example Comparative example One 2 3 4 One 2 3 4 5 Mooney viscosity (FMB) 95 96 97 98 95 93 94 92 90 △MV 48 46 49 47 49 47 48 46 47 Tensile properties M-300% 111 113 121 120 100 108 107 108 107 Tensile stress 120 116 114 115 100 106 109 107 106 Abrasion resistance 98 105 118 110 100 99 - 97 98 Viscoelastic properties Tanδ @ 0℃ 98 100 99 99 100 100 100 103 101 Tanδ @ 60℃ 104 104 107 106 100 103 101 99 100

In Table 2, the results of the tensile properties, abrasion resistance, and Tanδ values at 0° C. of Examples 1 to 4 and Comparative Examples 2 to 4 are calculated and indexed using Equation 2 below based on the measured values of Comparative Example 1. (index), Tanδ value at 60 ℃ was indexed by calculating by the following equation (3).

[Equation 2]

Index=(measured value/reference value)×100

[Equation 3]

Index=(reference value/measurement value)×100

As shown in Table 2, Examples 1 to 4 according to an embodiment of the present invention have excellent workability at an equivalent level compared to Comparative Examples 1 to 5, but have significantly increased tensile properties, abrasion resistance, and viscoelastic properties.

Specifically, Examples 1 to 3, while exhibiting excellent workability at an equivalent level or higher compared to Comparative Examples 3 to 5, in particular, tensile properties, abrasion resistance, and Tan δ values at 60°C were greatly improved. At this time, Comparative Examples 3 to 5 were used when the modifiers of Formula 1-1 used in Examples 1 to 3 were blended in the rubber composition. Through these results, the modified conjugated diene-based polymers according to the present invention were composed of the active polymer and Formula 1. It can be confirmed that the prepared denaturant is reacted to include a functional group derived from the denaturant in the polymer molecule, and thus, while having excellent processability, tensile properties, abrasion resistance, and viscoelastic properties can be significantly improved. In addition, it can be confirmed that such a remarkable effect is not expressed when the denaturant is applied when compounding the rubber composition.

Claims (12)

A modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by Formula 1 below:
[Formula 1]

In Chemical Formula 1,
R ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or a monovalent heterohydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O,
R ₂ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a divalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of aryl groups having 6 to 20 carbon atoms; Or a divalent heterohydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O,
R ₃ to R ₅ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and at least one of R ₃ to R ₅ is an alkoxy group having 1 to 20 carbon atoms.
The method according to claim 1,
In Chemical Formula 1,
R ₁ is 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, an arylalkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, A phenoxyalkyl group having 7 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, and -[R ¹¹ O]xR ¹² (where R ¹¹ is an alkylene group having 2 to 10 carbon atoms, R ¹² is a hydrogen atom, and 1 to 10 carbon atoms. Selected from the group consisting of an alkyl group, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms and an arylalkyl group having 7 to 18 carbon atoms, and x being an integer of 2 to 10) Phosphorus modified conjugated diene polymer.
The method according to claim 1,
In Chemical Formula 1,
R ₁ is 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, and a phenoxyalkyl group having 7 to 12 carbon atoms. It is any one selected from the group consisting of,
R ₂ is an alkylene group having 1 to 10 carbon atoms,
R ₃ to R ₅ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of R ₃ to R ₅ is a modified conjugated diene polymer having 1 to 10 carbon atoms.
The method according to claim 1,
The modified conjugate represented by Formula 1 is a modified conjugated diene-based polymer that is one selected from the group consisting of compounds represented by Formula 1-1 and Formula 1-2 below:
[Formula 1-1]

[Formula 1-2]

.

The method according to claim 1,
The polymer is a modified conjugated diene-based polymer containing a functional group derived from a modifier represented by Chemical Formula 1 in a side chain.
The method according to claim 1,
The polymer is a modified conjugated diene-based polymer containing a functional group derived from a modifier represented by Formula 1 at least at one end.
The method according to claim 1,
The polymer is a modified conjugated diene-based polymer having a denaturation rate of 5 mol% to 80 mol%.
1) polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent to prepare an active polymer; And
2) A method for preparing the modified conjugated diene-based polymer according to claim 1, comprising reacting the active polymer with a modifier represented by Chemical Formula 1:
[Formula 1]

In Chemical Formula 1,
R ₁ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or a monovalent heterohydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O,
R ₂ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a divalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of aryl groups having 6 to 20 carbon atoms; Or a divalent heterohydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom selected from the group consisting of N, S and O,
R ₃ to R ₅ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
The method according to claim 8,
The catalyst composition is a method for producing a modified conjugated diene-based polymer that is used in an amount such that the neodymium compound is 0.1 mmol to 0.5 mmol based on 100 g of a conjugated diene-based monomer.
The method according to claim 8,
The neodymium compound is a method of preparing a modified conjugated diene-based polymer that is a compound represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R _a to R _c are, independently of each other, hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, not all R _a to R _c are hydrogen at the same time.
The method according to claim 8,
The denaturing agent is a method for producing a modified conjugated diene-based polymer, which is used in a ratio of 0.5 mol to 20 mol based on 1 mol of the neodymium compound.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 1.