KR20210043830A - 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 compounding properties due to excellent affinity with a filler, a method for preparing the same, and a rubber composition comprising the same. Provided is a modified conjugated diene-based polymer, comprising: a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from a modifier represented by chemical formula 1.

Description

Modified conjugated diene polymer, a manufacturing method thereof, and a rubber composition containing the same TECHNICAL FIELD {MODIFIED CONJUGATED DIENE POLYMER, PREPARATION METHOD THEREOF AND RUBBER COMPOSITION COMPRISING THE SAME}

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 including the same.

In recent years, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene-based polymer having low running resistance, excellent abrasion resistance, and tensile properties as a rubber material for tires, and also having adjustment stability typified by wet skid resistance is required.

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

As rubber materials having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, and the like are known, but these have a problem with 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) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. .

When the above-described BR or SBR is used as a rubber material for a tire, a filler such as silica or carbon black is usually blended together to obtain the required properties of the tire. However, there is a problem in that physical properties including abrasion resistance, crack resistance or processability are deteriorated because the affinity between the BR or SBR and the filler is not good.

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

In addition, in a 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 a filler such as silica or carbon black, the living active end is determined by a specific modifier. A method of denaturation has been developed. However, in the case of a polymer whose terminal is modified, there is an advantage in that the affinity with the filler is improved and thus the blending properties, such as tensile properties and viscoelastic properties, are improved, but on the other hand, the blending processability is greatly reduced and thus processability is poor.

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

Therefore, when manufacturing SBR or BR, there is a demand for a method capable of improving processability while having excellent blending properties.

JP 5172663 B2

The present invention was devised to solve the problems of the prior art, and the modified conjugated diene system capable of improving the blending properties while maintaining excellent processability and abrasion resistance of the rubber composition when applied to a rubber composition due to its excellent filler affinity. It is an object to provide a polymer.

In addition, an object of the present invention is to provide a method for producing the modified conjugated diene 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 is a repeating unit derived from a conjugated diene-based monomer; And it provides a modified conjugated diene-based polymer comprising a functional group derived from a denaturant represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently substituted or unsubstituted 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 a divalent hydrocarbon 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 ₈ 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 _{8 is an alkoxy group having 1 to 20 carbon atoms.}

In addition, 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 it provides a method for producing the modified conjugated diene-based polymer comprising the step (step 2) of reacting the active polymer with a denaturant represented by Formula 1:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently substituted or unsubstituted 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 a divalent hydrocarbon 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 ₈ 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 _{8 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 binding a functional group derived from a denaturant represented by Formula 1 to the side chain of the polymer chain, and thus it is applied to a rubber composition to improve processability of the rubber composition and While maintaining excellent abrasion resistance, there is an effect that can greatly improve compounding properties such as 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 denaturant in the side chain of the polymer due to the reaction of the double bond in the active polymer and the azo group in the denaturant by denaturing the active polymer using a modifier represented by Formula 1 It is possible to easily prepare a modified conjugated diene-based polymer having a structure in which is bonded.

In addition, the rubber composition according to the present invention includes the modified conjugated diene-based polymer, thereby having excellent processability and abrasion resistance, and improving tensile properties and viscoelastic properties.

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 construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Hereinafter, the terms and measurement methods used in the present invention may be defined as follows unless otherwise defined.

[Terms]

The term'polymer' as used herein, whether of the same or different types, refers to a polymer compound prepared by polymerizing monomers. In this way the generic term polymer encompasses the term homopolymer and the term copolymer, which are commonly used to refer to polymers made from only one monomer.

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 exists in a functional group, atomic group, or compound when hydrogen of a functional group, atomic group or compound is substituted with a specific substituent. One or two or more substituents may be present depending on the number of hydrogens. In addition, when a plurality of substituents are present, each of the 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. It may represent a monovalent atomic group in which carbon and hydrogen are bonded, 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, a cycloalkyl containing one or more unsaturated bonds. It may represent a divalent atomic group in which carbon and hydrogen are bonded, such as an ene group and an arylene group, and the divalent atomic group may have a linear or branched structure depending on the structure of the bond.

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

The term'cycloalkyl 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 having one ring formed or a polycyclic aromatic hydrocarbon having two or more rings bonded thereto. aromatic hydrocarbon).

In the present invention, the term'alkenyl group' may mean a monovalent aliphatic unsaturated hydrocarbon containing one or two or more double bonds.

In the present invention, the term'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon containing one or two or more triple bonds.

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

In the present invention, the terms "derived repeating unit", "derived unit" and "derived functional group" may refer to a component, structure, or the substance itself derived from a substance.

The terms "comprising" and "having" and their derivatives in the present invention are not intended to exclude the presence of any additional components, steps or procedures, whether they are specifically disclosed or not. . For the avoidance of any uncertainty, all compositions claimed through the use of the term'comprising', whether polymer or otherwise, may contain any additional additives, adjuvants, or compounds, unless stated to the contrary. Can include. In contrast, the term'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except that it is not essential to operability. The term'consisting of' excludes any component, step or procedure not specifically described or listed.

[How to measure]

In the present invention, '1,4-cis bond content' and '1,2-vinyl bond content' can be measured by Fourier transform infrared spectroscopy (FT-IR), for example, 5 mg of carbon disulfide in the same cell as a blank. After measuring the FT-IR transmittance spectrum of the carbon disulfide solution of the conjugated diene-based polymer prepared at a concentration of /mL, ^{the maximum peak value around 1130 cm -1} of the measurement spectrum (a, baseline), trans-1,4 binding The minimum peak value (b) around 967 cm ^-1 representing 1,2-vinyl bonds, and the minimum peak value around ^{911 cm -1} representing 1,2-vinyl bonds (c), and around ^{736 cm -1 representing cis-1,4 bonds.} Each content was calculated using the minimum peak value (d) of.

The present invention provides a modified conjugated diene-based polymer that has excellent filler affinity and is suitable for rubber compositions and can greatly improve blending properties while maintaining excellent processability and abrasion resistance of the rubber composition.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a repeating unit derived from a conjugated diene-based monomer; And a functional group derived from a denaturant represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently substituted or unsubstituted 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 a divalent hydrocarbon 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 ₈ 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 _{8 is an alkoxy group having 1 to 20 carbon atoms.}

The modifier according to the present invention may be a compound represented by Formula 1 itself, or may include another compound capable of denaturing a conjugated diene-based polymer together with the compound represented by Formula 1.

Specifically, in Formula 1, R ₁ and R ₂ are each independently 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, or An unsubstituted C1-C20 divalent hydrocarbon group; Alternatively, it may be a divalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S, and O.

When each of R ₁ and R ₂ is an unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, each of R ₁ and 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, as a combination group thereof, it may be an arylalkylene group having 7 to 20 carbon atoms. Specifically, R ₁ and R ₂ may each independently be an alkylene group having 1 to 10 carbon atoms.

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

In addition, when each of R ₁ and R ₂ is a divalent hydrocarbon group having 1 to 20 carbon atoms including a hetero atom, each of R ₁ and R ₂ includes a hetero atom instead of at least one carbon atom in the hydrocarbon group, or ; Alternatively, at least one hydrogen atom bonded to a carbon atom in the hydrocarbon group may be substituted with a hetero atom or a functional group containing a hetero atom, wherein the hetero atom may be selected from the group consisting of N, O, and S.

Specifically, when each of R ₁ and R ₂ is a C 1 to C 20 divalent hydrocarbon group containing a hetero atom, an alkoxy group; Phenoxy group; Carboxyl group; Acid anhydride group; Amino group; Amide group; Epoxy group; Mercapto group; An alkylene group having 1 to 10 carbon atoms, including at least one functional group selected from the group consisting of a hydroxy group, an alkoxy group, a phenoxy group, a carboxy group, an ester group, an acid anhydride group, an amino group, an amide group, an epoxy group and a mercapto group, and 6 to 20 carbon atoms 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 ₈ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, but at least one of _{R 3} to R _{8 may be an alkoxy group having 1 to 20 carbon atoms.} Specifically, the R ₃ to R ₈ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, _{but at least one of R 3} to R ₅ and at least one of R ₆ to R ₈ have 1 to 10 carbon atoms. It may be an alkoxy group of.

_{In addition, R 1} and R ₂ in Formula 1 according to an embodiment of the present invention are each independently an alkylene group having 1 to 10 carbon atoms, and R ₃ to R ₈ are each independently an alkyl group having 1 to 10 carbon atoms or 1 It is an alkoxy group of to 10, but at least one of R ₃ to R ₅ and at least one of R ₆ to R ₈ may be an alkoxy group having 1 to 10 carbon atoms.

As a specific example, the modifier represented by Formula 1 may be one or more selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

.

.

The modifier according to an embodiment of the present invention may include a ketone group, an azo group, and an alkoxysilane group in the molecule, and the azo group exhibits high reactivity with a double bond in the polymer main chain, thereby forming a side chain in the polymer main chain. Derived functional groups can be introduced, and the alkoxysilane group can react with the active site at the end of the polymer main chain, thereby introducing a functional group derived from a denaturant at the end and side chain to denature the polymer with a high denaturation rate, and the ketone The group can increase the solubility of the denaturant by increasing the affinity for the polymerization solvent, and thereby facilitate the denaturation reaction, thereby improving the denaturation rate. In addition, the alkoxysilane group can improve the dispersibility of the filler by preventing aggregation between fillers in the rubber composition. For example, when silica, which is a kind of inorganic filler, is used as a filler, aggregation is likely to occur due to hydrogen bonds between hydroxyl groups present on the surface of the silica.The alkoxysilane group interferes with the hydrogen bonds between the hydroxyl groups of the silica, thereby dispersing the silica. Can be improved.

As such, the modifier has a structure capable of maximizing the blending properties of the modified conjugated diene polymer, and a modified conjugated diene polymer having excellent balance of mechanical properties such as abrasion resistance and processability of the rubber composition can be efficiently produced.

Meanwhile, in the modified conjugated diene-based polymer according to an embodiment of the present invention, the polymer may include a functional group derived from a modifier in a side chain. That is, the functional group derived from the denaturant may be a side chain bonded to the main chain constituting the polymer, and a specific example may have a structure represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁ to R ₈ are as defined in Formula 1, a and b represent the ratio of units constituting the polymer, and a+b may be 100 mol%.

Specifically, the denaturant represented by Formula 1 according to an embodiment of the present invention contains an azo group, a double bond in the polymer, that is, a double bond in the main chain consisting of a repeating unit derived from a conjugated diene-based monomer, and The azo group is reacted and a functional group derived from a denaturant is bonded as a side chain of the main chain to denature the conjugated diene polymer.

In addition, the polymer according to an embodiment of the present invention may include a functional group derived from a denaturant represented by 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 including a functional group derived from a denaturant in a side chain and a functional group derived from a denaturant in at least one terminal.

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

Here, the modification rate refers to the ratio of the unit derived from the conjugated diene-based monomer to which the functional group derived from the modifier represented by Formula 1 is bonded in the modified conjugated diene-based polymer, that is, the ratio of b in the above formula (2). It may be to represent.

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

[Equation 1]

Modification rate (%) = [(Peak area of units derived from conjugated diene-based monomers to which functional groups derived from denaturants are bonded)/(total peak area of modified conjugated diene-based polymers)] X 100

In addition, 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 contain 80 to 100% by weight of units derived from 1,3-butadiene monomers, and 20% by weight or less of units derived from other conjugated diene-based monomers that can be optionally copolymerized with 1,3-butadiene. In the above range, there is an effect that the content of 1,4-cis bonds in the polymer is not lowered. At this time, as the 1,3-butadiene monomer, 1,3-butadiene or derivatives thereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene And other conjugated diene-based monomers copolymerizable with the 1,3-butadiene include 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4 -Methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, and the like, and any one or two or more compounds of these 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 moiety 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) of 20 or more and 100 or less at 100°C, specifically 30 or more and 80 or less, and 35 or more and 75 or less. Or it may be 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 aforementioned range.

In the present invention, the Mooney viscosity was measured at 100° C. and a Rotor Speed of 2±0.02 rpm using a Mooney viscometer, for example, a Large Rotor of Monsanto's MV2000E. Specifically, after allowing the polymer to stand at room temperature (23±5°C) for 30 minutes or more, 27±3g was collected and filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating a platen.

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, 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 (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). At this time, the number average molecular weight (Mn) is the common average of the molecular weights of individual polymers calculated by measuring the molecular weights of n polymer molecules and dividing the total molecular weights by n, and the weight average molecular weight (Mw) is a polymer It shows the molecular weight distribution of the composition. All molecular weight averages can be expressed in grams per mole (g/mol). In addition, the weight average molecular weight and number average molecular weight may each mean a molecular weight in terms of polystyrene analyzed by gel permeation chromatography (GPC).

The modified conjugated diene-based polymer according to an embodiment of the present invention satisfies the above-described molecular weight distribution condition and may have a weight average molecular weight (Mw) of 3 X 10 ⁵ to 1.5 X 10 ⁶ g/mol, and a number average Molecular weight (Mn) may be 1.0 X 10 ⁵ to 5.0 X 10 ⁵ g/mol, and when applied to a rubber composition within this range, it has excellent tensile properties and excellent processability. It is easy, and there is an effect of excellent balance of mechanical properties and properties 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 is 1.5 X 10 ⁵ to 3.5 X, for example 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 satisfies the conditions of a weight average molecular weight (Mw) and a number average molecular weight together with the above molecular weight distribution, when applied to a rubber composition, It has excellent tensile properties, viscoelasticity and workability, and has an excellent balance of physical properties therebetween.

In addition, the conjugated diene-based polymer may have a cis-1,4 bond content of the conjugated diene portion measured by Fourier transform infrared spectroscopy (FT-IR) of 95% or more, more specifically 98% or more. Accordingly, when applied to a rubber composition, 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 5% or less, more specifically 2% or less of the conjugated diene portion measured by Fourier transform infrared spectroscopy. When the vinyl content in the polymer exceeds 5%, there is a concern that the abrasion resistance, crack resistance, and ozone resistance of the rubber composition including the same may be deteriorated.

In addition, the present invention provides a method for producing 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 denaturant represented by the following formula (1) (step 2).

[Formula 1]

In Formula 1, R ₁ to R ₈ are as defined above.

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

In the present invention, in the active polymer containing the organometallic moiety, 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), and an activated organometallic in the main chain. It may be an activated organometallic site in a site or a side chain (side chain). Among them, when an activated organometallic site of a conjugated diene-based polymer is obtained by anionic polymerization or coordination anion polymerization, the organometallic site is an activated organometallic at the terminal. It may represent a part.

The conjugated diene-based monomer is not particularly limited, but, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl The group consisting of -1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, etc. 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 a neodymium compound is 0.1 mmol to 0.5 mmol based on a total of 100 g of conjugated diene-based monomers, and specifically, the neodymium compound is based on a total of 100 g of conjugated diene-based monomers. It may be used in an amount of 0.1 mmol to 0.4 mmol, more specifically 0.1 mmol to 0.25 mmol.

The neodymium compound is its carboxylate (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2 -Ethylhexanoate, neodymium neodecanoate, etc.); Organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) Phosphate, or neodymium didecyl phosphate, etc.); Organic phosphonates (e.g., neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, Neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate); Organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methylheptyl) phosphinate, or Neodymium (2-ethylhexyl) phosphinate, etc.); Carbamates (eg, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate); Dithiocarbamate (eg, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate 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 allyloxides (eg, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.); Halides or pseudo halides (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide, etc.); Oxyhalides (eg, neodymium oxyfluoride, neodymium oxy chloride, or neodymium oxy bromide, etc.); Or an organic neodymium-containing compound containing one or more neodymium element-carbon bonds (e.g., Cp ₃ Nd, Cp ₂ NdR, Cp ₂ NdCl, CpNdCl ₂ , CpNd (cyclooctatetraene), (C ₅ Me ₅ ) ₂ NdR, NdR ₃ , Nd (allyl) ₃ , or Nd (allyl) ₂ Cl, and the like, R is a hydrocarbyl group), and the like, and any one or a mixture of two or more of them may be included.

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

[Formula 3]

In Formula 3, R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided _{that all of R a} to R _c are not 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 1 selected from the group consisting of, Nd (2,2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ It can be more than a species.

In addition, as another example, in consideration of excellent solubility in a solvent, conversion to catalytically active species, and excellent effect of improving catalytic activity without concern for oligomerization, the neodymium compound is more specifically represented by 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.

In a more specific example, in Formula 3, R _a is an alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R _b and R _c are It may not be hydrogen at the same time, and specific examples thereof include Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl decanoate) ₃ , Nd (2- Ethyl-2-butyl 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 3, among which Neodymium-based compounds are 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 It} may be one or more selected from the group consisting of.

More specifically, in 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 Formula 3 includes a carboxylate ligand containing an alkyl group having a length of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a three-dimensional change around the center of the neodymium metal. It is possible to block the coagulation phenomenon 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 a reduction in the proportion of neodymium located in a central portion where conversion to the catalytically active species is difficult, thereby increasing the conversion rate to the 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 the non-polar solvent at room temperature (25° C.).

In the present invention, the solubility of a neodymium-based compound refers to a degree of clear dissolution without a cloudy phenomenon, and excellent catalytic activity may be exhibited 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 reaction product has the effect of improving the solubility of the neodymium compound in a solvent by Lewis base and allowing it to be stored in a stable state for a long time. For example, the Lewis base may be used in a ratio of 30 moles or less, or 1 to 10 moles per 1 mole of the neodymium element. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organophosphorus compound, or a monohydric or dihydric alcohol.

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 may include a neodymium compound, and may further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer.

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

(a) alkylating agent

The alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and may serve as a cocatalyst. The alkylating agent may be used without particular limitation as long as it is used as an alkylating agent in the production of a diene-based polymer, and 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 containing.

Specifically, as the organic aluminum compound, 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; Diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, Diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride Ride, phenylisobutylaluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl- n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl 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. Hydride, etc. are mentioned. Examples of the organic magnesium compound include diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or alkyl magnesium compounds such as dibenzyl magnesium, and the like. Examples of the organolithium compound include alkyl lithium compounds such as n-butyllithium.

In addition, the organic aluminum compound may be aluminoxane.

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

[Formula 4a]

[Formula 4b]

In Formulas 4a and 4b, R is a monovalent organic group bonded to an aluminum atom through a carbon atom, and may be a hydrocarbyl group, and x and y are 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 methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n -Pentyl aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenylaluminoxane or 2,6- It may be dimethylphenyl aluminoxane and the like, and any one or a mixture of two or more of them may be used.

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

[Formula 5]

In 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 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. It is an alkyl group of to 10, and more specifically, it may be an isobutyl group.

More specifically, the modified methylaluminoxane may be obtained by substituting about 50 mol% to 90 mol% of the methyl group of methylaluminoxane with the hydrocarbon group described above. When the content of the substituted hydrocarbon group in the modified methylaluminoxane is within the above range, the catalytic activity may be increased by promoting alkylation.

Such modified methylaluminoxane may be prepared according to a conventional method, and specifically, may be prepared using trimethylaluminum and alkyl aluminum other than trimethylaluminum. 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 with respect to 1 mol of the neodymium compound. have. If the alkylating agent is included in a molar ratio of more than 200, it is not easy to control the catalytic reaction during the production of the polymer, and there is a concern that an excess of the alkylating agent may cause side reactions.

(b) halide

The halide is not particularly limited, for example, a halogen alone, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide or an organometallic halide, and any of these One or a mixture of two or more may be used. Among these, when considering the excellent effect of improving catalytic activity and thus improving reactivity, any one or a mixture of two or more selected from the group consisting of an organic halide, a metal halide, and an organometallic halide may be used as the halide.

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

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

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

In addition, as the organic halide, 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, propi Onyl 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, Benzoyl iodide, propionyl iodide, methyl iodoformate, etc. are mentioned.

In addition, as the non-metal halide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxychloride, 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 tetrachloride, arsenic triiodide, tellurium sayiodide, boron triiodide, phosphorus triiodide, selenium oxyiodide or phosphorus triiodide, etc. Can be mentioned.

In addition, as the metal halide, tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, Indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc iodide, tetraiodide Germanium, tin sayodine, tin iodide, antimony triiodide, or magnesium iodide.

In addition, the organometallic halide includes 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 dichloride. 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, ethyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride, trimethyl tin chloride, trimethyl tin bromide, triethyl tin chloride, triethyl tin 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 required Odide, n-butyl magnesium iodide, isobutyl magnesium iodide, phenyl magnesium iodide, benzyl magnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin required Odide, di-n-butyltin diiodide, di-t-butyltin diiodide, etc. are mentioned.

In addition, the catalyst composition according to an embodiment of the present invention contains the halide in 1 mol to 20 mol, more specifically 1 mol to 5 mol, more specifically 2 mol to 3 mol with respect to 1 mol of the neodymium compound. Can include. If the halide is contained in an amount exceeding 20 molar ratio, it is not easy to remove the catalytic reaction, and there is a concern that an excess halide may cause side reactions.

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, and is a tetraarylborate anion or fluorinated tetraaryl. It may be a borate anion and the like. In addition, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation together with the non-coordinating anion; It may include an ammonium cation such as an N,N-dialkyl anilinium cation, or a counter cation such as a phosphonium cation. More specifically, the compound containing the non-coordinating anion is triphenyl carbonium tetrakis (pentafluoro phenyl) borate, N,N-dimethylanilinium tetrakis (pentafluoro phenyl) borate, triphenyl carbonium tetra Kiss[3,5-bis(trifluoromethyl)phenyl]borate, or N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like.

In addition, as the non-coordinating anion precursor, a compound capable of forming a non-coordinating anion under reaction conditions, and a triaryl boron compound (BE ₃ , wherein E is a pentafluorophenyl group or a 3,5-bis(trifluoromethyl) phenyl group, etc. The same strong electron-attracting 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 by pre-mixing a part of the conjugated diene-based monomer used in the polymerization reaction with a polymerization catalyst composition. By using it in the form of a premix catalyst composition, not only can the catalyst composition activity be improved, but also the produced active polymer can be stabilized.

In the present invention, the "preforming" means a catalyst composition comprising a neodymium compound, an alkylating agent and a halide, that is, when the catalyst system includes diisobutylaluminum hydride (DIBAH), etc., various In order to reduce the possibility of generating active species in the catalyst composition, a small amount of conjugated diene monomers such as 1,3-butadiene are added, and it may mean that pre-polymerization is performed in the catalyst composition system with the addition of 1,3-butadiene. have. In addition, "premix" may mean a state in which polymerization is not performed in the catalyst composition system and each compound is uniformly mixed.

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

The catalyst composition according to an embodiment of the present invention includes at least one of the aforementioned neodymium compounds and alkylating agents, halides and conjugated diene-based monomers in organic solvents, specifically neodymium compounds, alkylating agents and halides, and optionally conjugated diene-based monomers. It can be produced by mixing monomers. In this case, the organic solvent may be a non-polar solvent that is not reactive with the constituents 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; Mixed solvents of aliphatic hydrocarbons having 5 to 20 carbon atoms such as petroleum ether, petroleum spirits, or kerosene; Alternatively, it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, xylene, and 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 C 5 to C 20 aliphatic hydrocarbon or a mixed solvent of aliphatic hydrocarbons, and more specifically, n-hexane, cyclohexane, or a mixture thereof. I 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, since the alkyl aluminoxane such as methylaluminoxane (MAO) or ethylaluminoxane as the alkylating agent is not easily dissolved in an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent may be appropriately used.

Further, when modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon-based solvent may be appropriately used. In this case, since it is possible to implement a single solvent system 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 the reactivity can be further improved by such catalytic activity.

Meanwhile, the organic solvent may be used in an amount of 20 to 20,000 moles, and more specifically, in an amount of 100 to 1,000 moles, based on 1 mole of the neodymium compound.

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

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

Here, the constant-temperature polymerization refers to a polymerization method comprising the step of polymerization by self-reaction heat without optionally applying heat after the catalyst composition is added, and the elevated temperature polymerization is a polymerization method in which heat is optionally applied after the catalyst composition is added to increase the temperature. The isothermal polymerization refers to a polymerization method in which heat is increased by applying heat after the catalyst composition is added, or a temperature of a reactant is maintained constant by taking away heat.

In addition, the polymerization may be performed using coordination anionic polymerization or 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 10°C to 120°C or 60°C to 90°C for 15 minutes to It can be done for 3 hours. If the polymerization temperature exceeds 200°C, it is difficult to sufficiently control the polymerization reaction, and the cis-1,4 bond content of the resulting conjugated diene-based polymer may be lowered. If the temperature is less than -20°C, polymerization There is a fear that the reaction rate and efficiency may decrease.

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

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

Typically, in the case of reacting an active polymer with a modifier, as described above, a modified polymer having an organometallic moiety at the end of the active polymer causes a reaction between the polymer end and the modifier, and thus a functional group derived from the modifier is bonded to the end of the polymer. Only can be manufactured.

However, in the manufacturing 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 is achieved by using a modifier represented by Formula 1 below. Occurs, and thus a functional group derived from a denaturant may also be bonded to the side chain of the polymer.

[Scheme 1]

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

Accordingly, the modified conjugated diene-based polymer prepared through the above production method according to an embodiment of the present invention may include a functional group derived from a modifying agent in the side chain of the polymer, and may include a functional group derived from a modifying agent at least at one end.

The modifier may be used in an amount of 0.5 to 20 moles relative to 1 mole of the neodymium compound in the catalyst composition. Specifically, the modifier may be used in an amount of 1 mol to 15 mol relative to 1 mol of the neodymium compound in the catalyst composition, and more specifically, 2 mol to 15 mol relative to 1 mol of the neodymium compound in the catalyst composition.

In addition, the denaturation reaction may be performed at 0°C to 90°C for 1 minute to 5 hours.

After the above-described modification reaction is completed, an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) or the like may be added to the polymerization reaction system to stop the polymerization reaction.

In the manufacturing method according to an embodiment of the present invention, after step 2, a modified conjugated diene-based polymer may be obtained through desolvation treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through supply of water vapor. . In addition, in the reaction product obtained as a result of the above reaction, an unmodified, active polymer may be included in addition to the above-described 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 contains a modified conjugated diene-based polymer in an amount of 0.1% by weight or more and 100% by weight or less, specifically 10% by weight to 100% by weight, and more specifically 20% by weight to 90% by weight. It may be to include. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, the effect of improving abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, and 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 in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be a natural rubber or a synthetic rubber, for example, the rubber component is a natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc. obtained by modifying or purifying 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, halogenated butyl rubber, and the like, and any one or a mixture of two or more of them may be used.

In addition, the rubber composition may include 0.1 parts by weight to 150 parts by weight of a filler based on 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 filler is not particularly limited, but may have a nitrogen adsorption specific surface area ( _{measured in accordance with 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 adsorption specific surface area of the carbon black ^{exceeds 250 m 2} /g, the processability of the rubber composition may be deteriorated, and when it is ^{less than 20 m 2} /g, the reinforcing 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, there is a concern that the processability of the rubber composition may be deteriorated, and when 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 a wet silica having the most remarkable effect of improving fracture properties and having both wet grip properties. In addition, the silica has a nitrogen surface area per gram (N ₂ SA) of 120 m2/g to 180 m2/g, and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) adsorption of 100 m2/g to 200 m2 May be /g. When the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, the reinforcing performance by silica may be deteriorated, and when it exceeds 180 m 2 /g, the workability of the rubber composition may be deteriorated. In addition, when the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by silica as a filler may be deteriorated, and when it exceeds 200 m 2 /g, the workability of the rubber composition may be reduced.

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

Specifically, as the silane coupling agent, 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-dimethylthiocarbamoyltetrasulfur 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 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, the required elastic modulus and strength of the vulcanized rubber composition can be secured, and at the same time, low fuel economy can be obtained.

In addition, in addition to the above components, the rubber composition according to an embodiment of the present invention includes various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, an anti-scorch agent, and a zinc white agent. ), stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is not particularly limited, and 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) may be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, and may specifically be a paraffinic, naphthenic, or aromatic compound, and more specifically, when considering tensile strength and abrasion resistance, the aromatic process oil price, hysteresis loss And when considering low-temperature characteristics, naphthenic or paraffinic process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and when included in the amount, it is possible to prevent a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

In addition, as the anti-aging agent, specifically, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- And oxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensation product of 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, or an internal mixer according to the above formulation, and has low heat generation and abrasion 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, pancreas, or bead coated rubber, and other tire members, anti-vibration rubber, belt conveyor, hose, etc. It may 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 for illustrative purposes only, and the scope of the present invention is not limited thereto.

Manufacturing Example 1

In an ice bath, 4.24 g of hydrazine dihydrochloride was added to a 250 ml round bottom flask, 80 ml of acetonitrile was added, and 11 ml of triethylamine was added. Subsequently, 20 g of 3-(triethoxysilyl)propyl isocyanate) was slowly added dropwise and reacted. Thereafter, the solid generated during the reaction was filtered to obtain a white solid.

The white solid was added to a 100 ml round bottom flask, _{50 ml of dichloromethane (CH 2} Cl ₂ ) and 3.7 ml of pyridine were sequentially added, and 6.8 g of N-bromosuccinimide was slowly added dropwise in an ice bath to react. Thereafter, water was added and the extraction process was performed. Separate the dichloromethane layer _{, add MgSO 4} to remove a small amount of water, remove MgSO ₄ through filtration, and remove the solvent using a rotary evaporator to obtain a red liquid from the formula 1-1. The indicated denaturant was obtained (yield 77%). ^By observing the 1 H nuclear magnetic resonance spectroscopy spectrum, the denaturant of Formula 1-1 was confirmed.

[Formula 1-1]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.4 (2H, s), 3.73 (12H, q), 2.96 (4H, t), 1.42 (4H, t), 1.13 (18H, t), 0.514 ( 4H, t).

Manufacturing Example 2

In an ice bath, 4.24 g of hydrazine dihydrochloride was added to a 250 ml round bottom flask, 80 ml of acetonitrile was added, and 11 ml of triethylamine was added. Subsequently, 23.5 g of 3-(triethoxysilyl)hexyl isocyanate) was slowly added dropwise and reacted. Thereafter, the solid generated during the reaction was filtered to obtain a white solid.

The white solid was added to a 100 ml round bottom flask, _{50 ml of dichloromethane (CH 2} Cl ₂ ) and 3.7 ml of pyridine were sequentially added, and 6.8 g of N-bromosuccinimide was slowly added dropwise in an ice bath to react. After that, water was added and the extraction process was performed. Separate the dichloromethane layer _{, add MgSO 4} to remove a small amount of water, remove MgSO ₄ through filtration, and remove the solvent using a rotary evaporator to obtain a red liquid, represented by the following formula 1-2. A denaturant was obtained (yield 80%). ^By observing the 1 H nuclear magnetic resonance spectroscopy spectrum, the denaturant of Formula 1-2 was confirmed.

[Formula 1-2]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.4 (2H, s), 3.73 (12H, q), 2.96 (4H, t), 1.45-1.50 (16H), 1.42 (4H, t), 1.13 ( 18H, t), 0.56 (4H, t).

Manufacturing Example 3

In an ice bath, 4.24 g of hydrazine dihydrochloride was added to a 250 ml round bottom flask, 80 ml of acetonitrile was added, and 11 ml of triethylamine was added. Then, 17 g of 3-(trimethoxysilyl)propyl isocyanate was slowly added dropwise to react. Thereafter, the solid generated during the reaction was filtered to obtain a white solid.

The white solid was put in a 100 ml round bottom flask, _{50 ml of dichloromethane (CH 2} Cl ₂ ) and 4 ml of pyridine were sequentially added, and 7.4 g of N-bromosuccinimide was slowly added dropwise in an ice bath to react. After that, water was added and the extraction process was performed. Separate the dichloromethane layer _{, add MgSO 4} to remove a small amount of water, remove MgSO ₄ through filtration, and remove the solvent using a rotary evaporator to obtain a red liquid, represented by the following formula 1-3. A denaturant was obtained (yield 50%). ^By observing the 1 H nuclear magnetic resonance spectroscopy spectrum, the denaturant of Formula 1-3 was confirmed.

[Formula 1-3]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.4 (2H, s), 2.96 (4H, t), 1.42 (4H, t), 1.13 (18H, t), 0.51 (4H, t).

Comparative Preparation Example 1

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

21 g of 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 to react. Thereafter, 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 the following formula (i) was obtained (yield 96%). ^By observing the 1 H nuclear magnetic resonance spectroscopy spectrum, the denaturant of the following formula (i) was confirmed.

[Formula i]

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).

Comparative Preparation Example 2

In an ice bath, 2.7 g of hydrazine dihydrochloride was added to a 100 ml round bottom flask, and 5.2 g of acetonitrile and triethylamine were sequentially added, and then 10 g of 2-ethylhexyl chloroformate was slowly added dropwise to react. . Thereafter, the solvent was removed using a rotary evaporator to obtain a white solid.

Into a 100 ml round-bottom flask, 9 g of the white solid was added, dichloromethane (CH ₂ Cl ₂ ) and 3.1 ml of pyridine were sequentially added, and 4.6 g of N-bromosuccinimide was slowly added dropwise in an ice bath to react. Thereafter, 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 the following formula (ii) was obtained (yield 85%). ^By observing the 1 H nuclear magnetic resonance spectroscopy spectrum, the denaturant of the following formula (ii) was confirmed.

[Formula ii]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 3.85-3.97 4 (4H, m), 1.37-1.53 (6H, m), 1.22-1.30 (12H, m), 0.88 (12H, m).

Example 1

After putting 900 g of 1,3-butadiene and 6,600 g of n-hexane into a 20L 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. At this time, the catalyst composition was added with neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay Co., Ltd. in an n-hexane solvent, and diisobutyl aluminum hydride (DIBAH), diethyl aluminum Chloride (DEAC) was sequentially added to the neodymium verserate:DIBAH:DEAC=1:16:2.4 molar ratio, followed by mixing to prepare. After adding the denaturant 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 hexane solution containing 1.0 g of a polymerization terminator and a solution of WINGSTAY (Eliokem SAS, France), an antioxidant, dissolved in 30% by weight in hexane, and the resulting heavy substance was heated with steam. It was put in hot water and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water to prepare a modified butadiene polymer.

Example 2

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

Example 3

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.

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 1-3 prepared in Preparation Example 3 was used instead of the modifier of Formula 1-1.

Comparative Example 1

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

Comparative Example 2

After putting 900 g of 1,3-butadiene and 6,600 g of n-hexane into a 20L 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. At this time, the catalyst composition was added with neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay Co., Ltd. in an n-hexane solvent, and diisobutyl aluminum hydride (DIBAH), diethyl aluminum Chloride (DEAC) was sequentially added so as to have a molar ratio of the neodymium verserate:DIBAH:DEAC=1:16:2.4, followed by mixing to prepare. Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution of WINGSTAY (Eliokem SAS, France), an antioxidant, dissolved in 30% by weight in hexane, and the resulting heavy substance was heated with steam. It was put in hot water and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water to prepare an unmodified butadiene polymer.

Comparative Example 3

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

Comparative 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 ii prepared in Comparative Preparation Example 2 was used instead of the modifier of Formula 1-1.

Experimental Example 1

Each of the physical properties was measured in the following manner for the Examples and Comparative Examples, 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 the condition of 40° C., and then loaded and flowed through gel permeation chromatography (GPC). At this time, the column was a combination of two PLgel Olexis columns and one PLgel mixed-C column manufactured by Polymer Laboratories. In addition, all of the newly replaced columns used a mixed bed type column, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

2) Mooney viscosity (RP, Raw polymer)

For each polymer, Mooney viscosity (ML1+4, @100°C) (MU) was measured at 100°C using a Large Rotor with Monsanto's MV2000E at 2±0.02 rpm of a Rotor Speed. At this time, the sample used was left at room temperature (23±3℃) for at least 30 minutes, then 27±3g was collected and filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating a platen.

division Example Comparative example One 2 3 4 One 2 3 4 GPC results Mn (x10 ⁵ g/mol) 1.93 2.07 2.11 2.05 2.64 2.13 1.93 2.10 Mw (x10 ⁵ g/mol) 4.73 4.84 4.50 4.70 6.18 4.92 4.73 4.82 MWD(Mw/Mn) 2.45 2.55 2.32 2.50 2.35 2.31 2.45 2.30 Mooney viscosity (RP) (ML1+4, @100℃)(MU) 49 50 48 52 48 46 47 45

Experimental Example 2

After preparing a rubber composition and a rubber specimen using the polymers of Examples and Comparative Examples, Mooney viscosity, tensile stress, 300% modulus, abrasion resistance, and viscoelastic properties were measured in the following manner. The results are shown in Table 2 below.

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

1) Preparation of rubber composition and rubber specimen

Examples and Comparative Examples: 100 parts by weight of each polymer, 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO), and stearic acid. ) Each rubber composition was prepared by mixing 2 parts by weight. 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 of the rubber compositions, and gently mixed at 50 rpm for 1.5 minutes at 50° C., and then a roll of 50° C. was used. Thus, a vulcanized formulation in the form of a sheet was obtained. The obtained vulcanized compound was vulcanized at 160° C. for 25 minutes to prepare a rubber specimen.

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

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

In addition, the Mooney viscosity of each polymer shown in Table 1 and the difference in Mooney viscosity of the blend (ΔMV, FMB-RP) were calculated, and the smaller the difference in Mooney viscosity, the better the processability.

3) tensile stress and 300% modulus

After vulcanizing each of the rubber compositions at 150° C. for t90 minutes, the tensile stress of the vulcanized material and the 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 according to ASTM D5963, and expressed as DIN wt loss index (loss volume index: ARIA (Abrasion resistance index, Method A)).

5) Viscoelastic properties

The most important properties of Tan δ for low fuel efficiency were measured by using DMTS 500N from Gabo, Germany, and the viscoelastic modulus (Tan δ) at -60℃~60℃ at a frequency of 10㎐, Prestrain 3%, and Dynamic Strain 3%. At this time, the Tanδ value at 0°C represents the wet road surface resistance, and the Tanδ value at 60°C represents the rolling resistance characteristics (fuel economy).

division Example Comparative example One 2 3 4 One 2 3 4 Mooney viscosity (FMB) 93 96 97 98 95 93 95 94 △MV 44 48 49 47 49 47 48 49 Tensile properties M-300% 116 120 113 118 100 108 111 102 Tensile stress 110 120 111 115 100 106 120 101 Wear resistance 100 105 100 110 100 99 98 99 Viscoelastic properties Tanδ @ 0℃ 100 105 99 99 100 100 98 96 Tanδ @ 60℃ 113 120 115 122 100 103 104 99

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

[Equation 2]

Index=(measured value/reference value)*100

[Equation 3]

Index=(reference value/measured value)*100

As shown in Table 2, it can be seen that Examples 1 to 4 have excellent workability equal to or higher than Comparative Examples 1 to 4, while both tensile properties, abrasion resistance, and viscoelastic properties are significantly superior.

Specifically, Examples 1 to 4 have equivalent or more workability and improved wear resistance and wet road surface resistance (0°C Tan δ value) than Comparative Example 2, while tensile properties are 5% or more, and rolling resistance (60°C Tan δ value) is All were significantly increased to more than 10%, and Comparative Example 2 was an unmodified butadiene polymer prepared under the same conditions as Examples 1 to 4, except that the denaturing reaction was not performed with the denaturing agent presented in the present invention. The modified conjugated diene-based polymer according to an embodiment of the present invention includes a functional group derived from a modifier represented by Formula 1, so that processability, tensile properties, abrasion resistance, and viscoelastic properties are all balanced, and in particular, tensile properties and viscoelastic properties are improved. It can be confirmed that there is.

In addition, Examples 1 to 4 exhibited greater than or equal to the workability, tensile properties and wet road surface resistance compared to Comparative Example 3, while the rotational resistance was significantly increased, and compared to Comparative Example 4, while exhibiting the same or more workability and wet road surface resistance, tensile properties, abrasion resistance, and rotation Resistance has been greatly increased. At this time, Comparative Examples 3 and 4 are modified butadiene polymers prepared under the same conditions as in Examples 1 to 4, except that a compound having only one alkoxysilane group or not as a modifier was used, through which the modified conjugated diene of the present invention The polymer is applied to a rubber composition by containing a functional group derived from a modifier represented by Formula 1 in which a ketone group and an alkoxysilane group are bonded to both sides of an azo group, thereby improving the processability, tensile properties, abrasion resistance and viscoelastic properties of the rubber composition. You can see that there is.

Claims (15)

A repeating unit derived from a conjugated diene-based monomer; And
A modified conjugated diene-based polymer containing a functional group derived from a denaturant represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently substituted or unsubstituted 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 a divalent hydrocarbon 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 ₈ 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 _{8 is an alkoxy group having 1 to 20 carbon atoms.}
The method of claim 1,
In Formula 1,
R ₁ and R ₂ are each independently an alkylene group having 1 to 10 carbon atoms,
R ₃ to R ₈ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, but at least one of _{R 3} to R _{5 and at least one of R 6} to R ₈ is an alkoxy group having 1 to 10 carbon atoms. The modified conjugated diene-based polymer.
The method of claim 1,
The modified conjugated diene polymer represented by Formula 1 is one selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

.
The method of claim 1,
The polymer is a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by Formula 1 in the side chain.
The method of claim 1,
The polymer is a modified conjugated diene-based polymer containing a functional group derived from a denaturant represented by Formula 1 at least at one end.
The method according to claim 1,
A modified conjugated diene-based polymer having a cis 1,4-bond content of 95% by weight or more.
1) 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; And
2) A method for producing a modified conjugated diene-based polymer according to item 1, comprising reacting the active polymer with a denaturant represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently substituted or unsubstituted 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 a divalent hydrocarbon 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 ₈ 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 _{8 is an alkoxy group having 1 to 20 carbon atoms.}
The method of claim 7,
The method for producing a modified conjugated diene-based polymer wherein the denaturant represented by Formula 1 is one selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

.
The method of claim 7,
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 to 0.5 mmol based on 100 g of a conjugated diene-based monomer.
The method of claim 7,
The neodymium compound is a method for producing 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 each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, _{not all of R a} to R _c are hydrogen at the same time.
The method of claim 7,
The method for producing a modified conjugated diene-based polymer is used in an amount of 0.5 to 20 moles based on 1 mole of the neodymium compound.
The method of claim 7,
The method for producing a modified conjugated diene-based polymer further comprising at least one of the catalytic alkylating agent, a halide, and a conjugated diene-based monomer.
A rubber composition comprising the modified conjugated diene polymer and a filler according to claim 1.
The method of claim 13,
100 parts by weight of the modified conjugated diene-based polymer; And 0.1 parts by weight to 150 parts by weight of a filler.
The method of claim 13,
The rubber composition that the filler is a silica-based filler or carbon black.