KR20200086533A - Modified conjugated diene polymer, preparation method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a high molecular weight modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition comprising the same. The modified conjugated diene-based polymer may have a high molecular weight because a polymer main chain constituting the polymer is crosslinked by a functional group derived from a modifier represented by chemical formula 1, and thus has excellent mechanical properties such as tensile properties and wear resistance. Also, the modified conjugated diene-based polymer has the functional group derived from the modifier, and thus can be applied to a rubber composition to have excellent processability and excellent blending properties such as viscoelastic properties.

Description

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

The present invention relates to a high molecular weight modified conjugated diene-based polymer, a method for manufacturing the same, and a rubber composition comprising the same.

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

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

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

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

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

In addition, in the living polymer obtained by coordination polymerization using a catalyst composition containing a neodymium compound as a method for increasing the dispersibility of a filler such as BR and silica or carbon black, a method of modifying the living active end with a specific modifier It was developed. However, in the case of a polymer having a modified terminal, there is an advantage that the affinity with the filler is improved to improve the compounding properties, such as tensile properties and viscoelastic properties, whereas the compounding processability is greatly reduced, resulting in poor processability.

In addition, the living polymer obtained by coordination polymerization using the catalyst composition containing the neodymium compound is induced to bond between polymer chains constituting the polymer using a coupling agent such as tin chloride (SnCl ₄ ) to increase molecular weight to increase mechanical properties. Methods to improve have been studied, but are limited due to the toxicity of tin.

JP 5172663 B2

The present invention has been devised to solve the problems of the prior art, having a high molecular weight improves mechanical properties such as tensile properties and abrasion resistance, and includes modified group-derived functional groups to improve compounding properties such as viscoelastic properties. It is an object to provide a diene-based polymer.

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

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

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

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₃ are, independently of each other, a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or -COOR ₄ , wherein R ₄ is an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, R ₂ is an alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. It is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with one or more substituents selected from the group consisting of aryl groups.

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

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₃ are, independently of each other, a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or -COOR ₄ , wherein R ₄ is an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, R ₂ is an alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. It is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with one or more substituents selected from the group consisting of aryl groups.

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 can have a high molecular weight by crosslinking the polymer main chain constituting the polymer with a functional group derived from the modifier represented by Formula 1, and thus has excellent mechanical properties such as tensile properties and wear resistance. can do.

In addition, the modified conjugated diene-based polymer according to the present invention is applied to a rubber composition by introducing a functional group derived from a modifying agent between chains at the same time that the polymer chain is crosslinked by a functional group derived from a denaturing agent, and is excellent in processability, but has compounding properties such as viscoelastic properties. This can be excellent.

In addition, in the method for preparing the modified conjugated diene-based polymer according to the present invention, each of the two azo groups in the denaturant reacts with a double bond in the polymer chain by using a denaturant represented by Formula 1 containing two azo groups, thereby inter-polymer chain Crosslinking can be induced, and at the same time, a high molecular weight modified conjugated diene-based polymer having a structure in which a functional group derived from a modifier is introduced between the polymer chains can be easily produced.

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

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

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

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

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

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

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

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

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

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

The present invention provides a modified conjugated diene polymer having excellent mechanical properties such as tensile properties and abrasion resistance by having a high molecular weight, and excellent compounding properties such as viscoelastic properties by including a functional group derived from a modifier.

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

[Formula 1]

In Chemical Formula 1,

R ₁ and R ₃ are, independently of each other, a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or -COOR ₄ , wherein R ₄ is an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, R ₂ is an alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. It is a divalent hydrocarbon group having 1 to 20 carbon atoms which is unsubstituted or substituted with one or more substituents selected from the group consisting of aryl groups.

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

Specifically, in Formula 1, R ₁ and R ₃ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or -COOR ₄ .

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

In addition, when R ₁ and R ₃ are each -COOR ₄ , R ₄ may be an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, and specifically, R ₄ may have 1 to 10 carbon atoms. It may be an alkyl group, and more specifically, it may be a branched alkyl group having 3 to 10 carbon atoms.

In addition, in Chemical Formula 1, R ₂ is 1 to 20 carbon atoms 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. It may be a divalent hydrocarbon group.

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

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

In addition, in Formula 1 according to an embodiment of the present invention, R ₁ and R ₃ are any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -COOR ₄ at the same time, wherein In R ₄ is an alkyl group having 1 to 10 carbon atoms, and R ₂ may be an alkylene 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 Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

.

.

The denaturant according to an embodiment of the present invention is a nitroxyl group (nitroxyl group) on both sides with an aliphatic hydrocarbon group; Azo group; And a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or an ester group. The azo group exhibits high reactivity with a double bond present in a polymer chain constituting the polymer, thereby providing two azo groups in the modifier. Each can react with the double bond of the polymer chain to crosslink the two polymer chains, thereby improving the molecular weight of the modified conjugated diene polymer to improve mechanical properties such as tensile and abrasion resistance.

In addition, the modifier according to an embodiment of the present invention while inducing cross-linking between polymer chains by an azo group, a modifier-derived functional group between polymer chains, such as a divalent aliphatic hydrocarbon group; Nitroxyl group; And a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or an ester group, to denature the polymer, and the aliphatic and aromatic hydrocarbon groups can increase the affinity for the polymerization solvent to increase the solubility of the modifier and thereby modify the reaction. It can be done easily. In addition, the ester group can improve the stability of the modifier by reducing the electron density of the azo group.

That is, the modifier according to an embodiment of the present invention may act as a crosslinking agent for crosslinking a polymer chain by including two azo groups, while simultaneously acting as a modifier for modifying the properties of the polymer by introducing functional groups into the polymer chain.

More specifically, in the modified conjugated diene-based polymer according to an embodiment of the present invention, the polymer includes a polymer chain comprising at least two conjugated diene-based monomer derived units, and the two polymer chains are represented by Formula 1 It may be crosslinked by a functional group derived from the denaturant displayed.

Specifically, it will be described through Formula 2 below.

[Formula 2]

In Chemical Formula 2, R ₁ to R ₃ are as defined in Chemical Formula 1.

Typically, the polymer is an aggregate of polymer chains formed by connecting units, and the conjugated diene-based polymer in the present invention may represent an aggregate of polymer chains composed of a unit derived from a conjugated diene-based monomer.

Specifically, the modifier represented by Chemical Formula 1 according to an embodiment of the present invention is a material having azo groups bonded to both sides around an aliphatic hydrocarbon group, and the azo groups in the modifier are composed of conjugated diene-based monomer derived units Polymer represented by the formula (2), which can exhibit high reactivity with a double bond in the polymer chain, and each azo group in the denaturant reacts with two polymer chains, thereby crosslinking the two polymer chains with a functional group derived from the denaturant. Chain units can be formed.

That is, the modified conjugated diene-based polymer according to an embodiment of the present invention includes a polymer chain unit having a structure represented by Formula 2, or a structure in which all polymer chains constituting the polymer are represented by Formula 2 It may be forming a polymer chain unit of.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may include a functional group derived from a modifier represented by Chemical Formula 1 in a polymer side chain. Specifically, as identified in the polymer chain unit represented by the formula (2), in the present invention, the functional group derived from the denaturant is present between the polymer chains and serves as a cross-linking link between the polymer chains. It may be bound to.

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

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

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

The modified conjugated diene-based polymer according to an embodiment of the present invention may have a weight average molecular weight (Mw) of 200,000 g/mol to 1,500,000 g/mol, and a number average molecular weight (Mn) of 50,000 g/mol to 1,000,000 g/ It may be mol, and when applied to a rubber composition within this range, it has excellent tensile properties and excellent workability, so it is easy to knead kneading due to improvement in workability of the rubber composition, and has an excellent effect on balance of mechanical properties and physical properties of the rubber composition. . The weight average molecular weight may be specifically 300,000 g/mol to 1,200,000 g/mol, or 500,000 g/mol to 1,000,000 g/mol, and the number average molecular weight is, for example, 100,000 g/mol to 800,000 g/mol, or 200,000 g /mol to 500,000 g/mol.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1.2 to 4.0, and more specifically, may have a molecular weight distribution of 1.5 to 3.5, 1.7 to 3.2 or 1.8 to 3.0.

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

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

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

In the present invention, the Mooney viscosity was measured under conditions of 100° C. and Rotor Speed 2±0.02 rpm using a Mooney viscometer, for example, a large rotor of MV2000E manufactured by Monsanto. Specifically, 37.3 parts by weight of TDAE (treated distillate aromatic extracted) oil, which is a process oil, is added to the polymer to mix it with 100 parts by weight of the polymer, and after mixing for 30 minutes or more at room temperature (23±5°C), 27±3 g is collected and die Mooney viscosity is measured by applying torque by filling the inside of the cavity and operating the platen.

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

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

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

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

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

[Formula 1]

In Chemical Formula 1, R ₁ to R ₃ are as defined above.

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

In the present invention, in the active polymer containing the organometallic moiety, the organometallic moiety may be an activated organometallic moiety at the end of the conjugated diene polymer (an activated organometallic moiety at the molecular chain end), among them anionic polymerization or When the activated organometallic part of the conjugated diene-based polymer is obtained by coordination anionic polymerization, the organometallic part may indicate an activated organometallic part at the terminal.

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

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

The catalyst composition may be used in an amount such that the neodymium compound is 0.02 mmol to 1.0 mmol based on 100 g of the conjugated diene-based monomer, and specifically, the neodymium compound is based on the total of 100 g of the conjugated diene-based monomer. It may be used in an amount such that 0.1 mmol to 0.5 mmol, more specifically 0.1 mmol to 0.25 mmol.

The neodymium compound is a carboxylate thereof (for example, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium sulphate, neodymium maleate, neodymium oxalate, neodymium 2 -Ethyl hexanoate, neodymium neo decanoate, etc.); Organophosphates (e.g. neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis (1-methyl heptyl) phosphate, neodymium bis (2-ethylhexyl) Phosphate, or neodymium didecyl phosphate, etc.); Organic phosphonates (e.g. neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, Neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate, etc.); Organic phosphinates (e.g. neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methyl heptyl) phosphinate or Neodymium (2-ethylhexyl) phosphinate, etc.); Carbamate (eg, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate); Dithio carbamate (eg, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithio carbamate or neodymium dibutyldithiocarbamate); Xanthogenates (eg, neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl xanthogenate, or neodymium benzyl xanthogenate); β-diketonate (eg, neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl acetonate, etc.); Alkoxides or allyl oxides (eg, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide); Halides or pseudohalides (such as neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); Oxyhalides (eg, neodymium oxyfluoride, neodymium oxy chloride, or neodymium oxy bromide, etc.); Or an organic neodymium compound containing one or more rare earth element-carbon bonds (e.g., Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn (cyclooctatetraene), (C ₅ Me ₅ ) ₂ LnR , LnR ₃ , Ln (allyl) ₃ , or Ln (allyl) ₂ Cl, wherein Ln is a rare earth metal element, and R is a hydrocarbyl group). It can contain.

Specifically, the neodymium compound may include a neodymium compound represented by Formula 3 below.

[Formula 3]

In the formula (3), R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided that R _a to R _c are not all hydrogen at the same time.

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

In addition, in another example, considering the excellent solubility in a solvent without concern about oligomerization, the conversion rate to catalytically active species, and thus the effect of improving catalytic activity, the neodymium compound is more specifically R _a in Formula 3 It is an alkyl group having 4 to 12 carbon atoms, and R _b and R _c are 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, but may be a neodymium-based compound.

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

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

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

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

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

In addition, the neodymium compound according to an embodiment of the present invention may be used in the form of a reactant with a Lewis base. This reactant has an effect of improving the solubility of the neodymium compound in a solvent by a Lewis base and storing it in a stable state for a long time. The Lewis base may be used, for example, in a proportion of 30 moles or less per mole of rare earth elements, or 1 to 10 moles. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organophosphorus compound, monovalent or divalent alcohol, or the like.

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

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

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

(a) Alkylating agent

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

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

In addition, the organoaluminum compound may be aluminoxane.

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

[Formula 4a]

[Formula 4b]

In the formulas 4a and 4b, R is a monovalent organic group that is attached to an aluminum atom through a carbon atom, and may be a hydrocarbyl group, and x and y are each independently an integer of 1 or more, specifically 1 to 100 , More specifically, it may be an integer of 2 to 50.

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

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

[Formula 5]

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

Specifically, in Formula 5, R is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may be an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an allyl group or an alkynyl group having 2 to 20 carbon atoms, and more specifically, 2 carbon atoms such as an ethyl group, an isobutyl group, a hexyl group, or an octyl group. To 10 alkyl groups, and more specifically, may be an isobutyl group.

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

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

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

(b) halide

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

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

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

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

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

In addition, the non-metal halide includes phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl ₄ ), silicon tetrabromide , Arsenic trichloride, Arsenic tribromide, Selenium tetrachloride, Selenium tetrabromide, Tellurium tetrachloride, Tellurium tetrabromide, Silicon tetraiodide, Arsenic triiodide, Arsenic iodide, Tellurium tetraiodide, Boron triiodeide, Phosphorus triiodide, Phosphorus iodinide Can be heard.

Further, the metal halide includes tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony trichloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, Indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiodide, gallium iodide, indium triiodide, indium iodide, titanium iodide, zinc iodide And germanium, tin iodide, tin iodide, antimony triiodide, or magnesium iodide.

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

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

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

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

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

(c) conjugated diene monomer

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

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

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

The catalyst composition according to an embodiment of the present invention is at least one of the above-mentioned neodymium compounds and alkylating agents, halides and conjugated diene-based monomers in an organic solvent, specifically, neodymium compounds, alkylating agents and halides, and optionally conjugated diene-based It can be prepared by mixing monomers. At this time, the organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition. Specifically, the non-polar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo Linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; A mixed solvent of an aliphatic hydrocarbon having 5 to 20 carbon atoms, such as petroleum ether or petroleum spirits, or kerosene; Or it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, xylene, or the like, and any one or a mixture of two or more of them may be used. More specifically, the non-polar solvent may be a linear, branched or cyclic aliphatic hydrocarbon or a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, and more specifically, n-hexane, cyclohexane, or a mixture thereof. Can.

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

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

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

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

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

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

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

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

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

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

Step 2 is a step of preparing a modified conjugated diene-based polymer containing a functional group by denaturing 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 the active polymer with the modifier, as described above, the organometallic moiety is present at the end of the active polymer, so that the reaction between the polymer end and the modifier occurs, and thus the modified polymer having a structure in which the modifier-derived functional group is bonded to the end of the polymer Only can be manufactured.

However, in the preparation method according to an embodiment of the present invention, the reaction of the double bond in the polymer chain composed of the unit derived from the conjugated diene-based monomer and the azo group in the denaturant as shown in Reaction Scheme 1 by using the denaturant represented by Formula 1 It is possible to produce a modified conjugated diene-based polymer having a structure in which the denaturant-derived functional group is bonded to the side chain of the polymer chain while the functional group derived from the denaturant exists as a linking group connecting polymer chains.

[Scheme 1]

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

The denaturing agent may be used in an amount of 0.1 to 10.0 parts by weight based on 100 parts by weight of the conjugated diene-based monomer, and specifically, the denaturing agent may be used in an amount of 1 to 5 parts by weight compared to 100 parts by weight of the conjugated diene-based monomer.

In addition, the denaturing agent may be used in 0.5 mol to 20 mol compared to 1 mol of the neodymium compound in the catalyst composition. Specifically, the denaturing agent may be used in a mole ratio of 1 to 15 moles compared to 1 mole of the neodymium compound in the catalyst composition.

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

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

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

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

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

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

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

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

The carbon black-based filler is not particularly limited, but may have, for example, a nitrogen adsorption specific surface area (measured according to N ₂ SA, JIS K 6217-2:2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutylphthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. When the nitrogen black specific surface area of the carbon black exceeds 250 m ² /g, the workability of the rubber composition may be deteriorated, and if it is less than 20 m ² /g, the reinforcement performance by the carbon black may be insignificant. In addition, when the DBP oil absorption amount of the carbon black exceeds 200 cc/100 g, the workability of the rubber composition may be deteriorated, and if it is less than 80 cc/100 g, the reinforcing performance by the carbon black may be insignificant.

In addition, the silica is not particularly limited, but may be, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica may be wet silica having the most remarkable effect of improving the fracture properties and the compatibility of wet grip. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen surface area per gram, N ₂ SA) of 120 m 2 /g to 180 m 2 /g, and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 m 2 /g to 200 m 2 /g. If the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, there is a fear that the reinforcing performance by the silica is lowered, and when it exceeds 180 m 2 /g, the workability of the rubber composition may be lowered. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, there is a fear that the reinforcing performance by the silica, which is a filler, may decrease, and if it exceeds 200 m 2 /g, the workability of the rubber composition may decrease.

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

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

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

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

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

The vulcanization accelerator is not particularly limited, specifically M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. A thiazole-based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, specifically, may be a paraffin-based, naphthenic-based, or aromatic-based compound, and more specifically, considering the tensile strength and abrasion resistance, the aromatic-based process oil, hysteresis loss And when considering low-temperature properties, naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, and when included in the content, the tensile strength of the vulcanized rubber, low heat generation (low fuel consumption) can be prevented from falling.

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

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

Accordingly, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreatic, or bead coated rubber, each member of a tire, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture of various industrial rubber products.

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

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are intended to illustrate the present invention, but the scope of the present invention is not limited to them.

Preparation Example 1

In an ice bath, 5 g of hexamethylene diisocyanate was added to a 100 ml round-bottom flask, acetonitrile was added, and 6.19 g of ethyl carbazate was slowly added dropwise thereto. Thereafter, a solvent was removed using a rotary evaporator to obtain a white solid.

11 g of the white solid was added to a 100 ml round-bottom flask, and dichloromethane (CH ₂ Cl ₂ ) and pyridine 6.0 ml were sequentially added to dissolve the solid, and reacted slowly while dropping 10.6 g of N-bromosuccinimide in an ice bath. Ordered. Thereafter, the solvent was removed using a rotary evaporator, dissolved in dichloromethane and extracted with water to obtain 11 g of a denaturant represented by Chemical Formula 1-1, which is a yellow solid (yield 91%). ^{The 1} H nuclear magnetic resonance spectroscopy spectrum was observed to confirm the denaturant represented by the following Chemical Formula 1-1.

[Formula 1-1]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 9.11 (2H, t), 4.46 (4H, q), 3.23 (4H, q), 1.52 (4H, d), 1.34 (10H, t).

Preparation Example 2

In an ice bath, 5 g of hexamethylene diisocyanate was added to a 100 ml round-bottom flask, acetonitrile was added, and 6.43 g of phenylhydrazine was slowly added dropwise. Thereafter, a solvent was removed using a rotary evaporator to obtain a white solid.

11.4 g of the white solid was added to a 100 ml round-bottom flask, and dichloromethane (CH ₂ Cl ₂ ) and 6.0 ml of pyridine were sequentially added to dissolve the solid, and slowly reacted while slowly adding 10.6 g of N-bromosuccinimide in an ice bath. Ordered. Thereafter, the solvent was removed using a rotary evaporator, dissolved in dichloromethane, and extracted with water to obtain 11 g of a yellow solid, a modifier represented by Chemical Formula 1-2 (yield 97%). ¹ H nuclear magnetic resonance spectroscopy spectrum was observed to confirm the denaturant of Formula 1-2 below.

[Formula 1-2]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.56 (2H, t), 7.83 (4H, t), 3.25 (4H, d), 1.56 (4H, t).

Preparation Example 3

In an ice bath, add 100 g of hydrazine monohydrate to a 500 ml round-bottom flask, add 125 ml of acetonitrile, and slowly 98 ml of 2-ethylhexyl chloroformate. It reacted while dropping. Thereafter, the solvent was removed using a rotary evaporator, and then dissolved by adding dimethyl ether, followed by extraction with NaHCO ₃ aqueous solution and separation to obtain a pink solution.

In a 100 ml round-bottom flask, 5 g of hexamethylene diisocyanate was added, acetonitrile was added, and 16.8 g of the pink solution was slowly added dropwise. Thereafter, a solvent was removed using a rotary evaporator to obtain a white solid.

In a 100 ml round-bottom flask, 15.8 g of the white solid was added, and 5.14 ml of dichloromethane (CH ₂ Cl ₂ ) and pyridine were sequentially added to dissolve the solid, and 10.3 g of N-bromosuccinimide was slowly added dropwise in an ice bath Ordered. Thereafter, the solvent was removed using a rotary evaporator, dissolved in dichloromethane, and extracted with water to obtain 13 g of a red color modifier represented by Chemical Formula 1-3 (yield 82%). The denaturants of the following Chemical Formula 1-3 were confirmed by observing the ¹ H nuclear magnetic resonance spectroscopic spectrum.

[Formula 1-3]

¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.59 (2H, s), 3.85-3.91 (4H, m), 2.95-2.99 (4H, m), 1.48 (2H, d), 1.22-1.36 (24H , m), 0.88 (12H, m).

Example 1

After adding 800 g of 1,3-butadiene and 5.4 kg of n-hexane to a 20 L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added thereto, polymerization was performed for 30 minutes. At this time, the catalyst composition is added to neodymium versatate (Nd(2-ethylhexanoate) ₃ ), Solvay) in n-hexane solvent, diisobutylaluminum hydride (DIBAH), diethylaluminum Chloride (DEAC) was prepared by sequentially adding to the molar ratio of neodymium versatate:DIBAH:DEAC=1:16:2.4, followed by mixing. After adding 6.5 mmol of the modifier of Formula 1-1 prepared in Preparation Example 1, a denaturation reaction was performed at 70° C. for 30 minutes (denaturant: 1,3-butadiene=3.5:100 parts by weight). Thereafter, the reaction was terminated by adding a solution in which 30 wt% of hexane solution containing 1.0 g of polymerization stopper and antioxidant WINGSTAY (Eliokem SAS, France) were dissolved in hexane, and the resulting heavy product was heated with steam. After stirring in hot water to remove the solvent, the roll was dried to remove the residual amount of solvent and water to prepare a modified butadiene polymer.

Example 2

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the modified agent of Formula 1-2 was used instead of the modified agent of Formula 1-1 (Modifier: 1,3-butadiene = 3.5: 100 parts by weight).

Example 3

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the modified agent of Formula 1-3 was used instead of the modified agent of Formula 1-1 (Modifier: 1,3-butadiene = 3.5: 100 parts by weight).

Comparative Example 1

As an unmodified butadiene polymer, CB29 (Lanxess Co.) was used as a comparative example.

Comparative Example 2

After adding 800 g of 1,3-butadiene and 5.4 kg of n-hexane to a 20 L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added thereto, polymerization was performed for 30 minutes. At this time, the catalyst composition is added to neodymium versatate (Nd(2-ethylhexanoate) ₃ ), Solvay) in n-hexane solvent, diisobutylaluminum hydride (DIBAH), diethylaluminum Chloride (DEAC) was prepared by sequentially adding to the molar ratio of neodymium versatate:DIBAH:DEAC=1:16:2.4, followed by mixing. Thereafter, the reaction was terminated by adding a solution in which 30 wt% of hexane solution containing 1.0 g of polymerization stopper and antioxidant WINGSTAY (Eliokem SAS, France) were dissolved in hexane, and the resulting heavy product was heated with steam. After stirring in hot water to remove the solvent, the roll was dried to remove the residual amount of solvent and water to prepare an unmodified butadiene polymer.

Experimental Example 1

The properties of the polymers of Examples 1 to 3 and Comparative Examples 1 and 2 were measured in the following manner, and the results are shown in Table 1 below.

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

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

2) Mooney viscosity (RP)

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

division Example Comparative example One 2 3 One 2 GPC results Mn(g/mol) 320,112 293,765 326,822 331,787 284,190 Mw (g/mol) 821,437 691,690 835,327 884,464 671,615 Mp(g/mol) 619,789 520,291 627,234 604,114 490,456 MWD (Mw/Mn) 2.56 2.35 2.56 2.67 2.36 Mooney viscosity (RP, ML1+4, @100℃) (MU) 35.0 40.0 38.1 39.9 43.1

As shown in Table 1, the polymers of Examples 1 to 3 had increased weight average molecular weight and number average molecular weight compared to the polymer of Comparative Example 2, except that the polymer of Comparative Example 2 was not subjected to denaturation reaction. It was manufactured through the same method as in Examples 1 to 3. This increase in molecular weight is a result showing that the polymers of Examples 1 to 3 are crosslinked by polymer chains by a functional group derived from a denaturant, and that a functional group derived from a denaturant is introduced.

Experimental Example 2

After preparing the rubber composition and the rubber specimen using the polymers of Examples 1 to 3, Comparative Examples 1 and 2, the Mooney viscosity, tensile stress, 300% modulus, abrasion resistance, and viscoelastic properties, respectively, were as follows. It was measured. The results are shown in Table 2 below.

In addition, in preparing the rubber composition and the rubber specimen, the polymer of Comparative Example 2 was mixed with the modifier of Chemical Formula 1-1 to represent Comparative Example 3.

(1) Preparation of rubber composition and rubber specimen

1) Examples 1 to 3, Comparative Examples 1 and 2

100 parts by weight of each polymer, 70 parts by weight of carbon black, 22.5 parts by weight of process oil (TDAE oil), 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid Each rubber composition was prepared by mixing parts. Thereafter, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ) and 0.5 parts by weight of vulcanization accelerator (DPG) were added to each rubber composition, and the mixture was gently mixed at 50 rpm for 50 minutes at 50°C, and then a roll of 50°C was used. Thus, a vulcanized compound in a sheet form was obtained. The obtained vulcanized formulation was vulcanized at 160°C for 25 minutes to prepare a rubber specimen.

2) Comparative Example 3

100 parts by weight of polymer of Comparative Example 2, 70 parts by weight of carbon black, 22.5 parts by weight of process oil (TDAE oil), 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO) and stearic acid ) 2 parts by weight of each rubber composition was prepared. Thereafter, 2 parts by weight of sulfur, 2 parts by weight of a vulcanization accelerator (CZ), 0.5 parts by weight of a vulcanization accelerator (DPG) and 3.5 parts by weight of a denaturant of Chemical Formula 1-1 were added to each rubber composition, and at 50 rpm for 1.5 minutes at 50°C. After mild mixing, a sheet-shaped vulcanization formulation was obtained using a roll at 50°C. The obtained vulcanized formulation 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 vulcanized formulation prepared above. Specifically, the Mooney viscosity (MV) was measured under the condition of Rotor Speed 2±0.02 rpm at 100°C using a large rotor with Monsanto MV2000E. At this time, the sample used was left for 30 minutes or more at room temperature (23±3℃), and then 27±3g was taken and filled inside the die cavity to operate the platen to measure the Mooney viscosity (FMB) while applying torque. Did.

In addition, the difference between the Mooney viscosity of each polymer shown in Table 1 and the Mooney viscosity of the formulation (ΔMV, FMB-RP) was calculated, and the smaller the Mooney viscosity difference, the better the processability. On the other hand, Comparative Example 3 is a composition obtained by mixing the polymer of Comparative Example 2 with a modifier of Formula 1-1, and the polymer Mooney viscosity of Comparative Example 3 is the same as that of Comparative Example 2.

(3) Tensile strength, tensile stress and 300% modulus

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

(4) Wear resistance (DIN wear test)

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

(5) Viscoelastic properties

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

division Example Comparative example One 2 3 One 2 3 Mooney viscosity (FMB) 77 75 79 78 76 77 △MV 39.8 38.9 40.9 38.1 43.1 39.0 Tensile properties
(Index, %) M-300% 102 101 105 100 95 98 The tensile strength 103 103 105 100 97 98 Wear resistance (Index, %) 107 105 110 100 95 96 Viscoelastic properties
(Index, %) Tanδ @ 0℃ 103 102 107 100 98 99 Tanδ @ 60℃ 102 100 101 100 99 100

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

[Equation 1]

Index=(measured value/reference value)×100

[Equation 2]

Index=(reference value/measurement value)×100

As shown in Table 2, it can be seen that Examples 1 to 3 are excellent in both tensile properties, abrasion resistance, and viscoelastic properties while having excellent workability equal to or greater than Comparative Examples 1 to 3.

Specifically, Examples 1 to 3, while having improved processability compared to Comparative Example 2, tensile properties, abrasion resistance, and viscoelastic properties (0° C. Tan δ value) all became remarkable at 5% or more, wherein Comparative Example 2 is the present invention Unmodified butadiene polymer prepared under the same conditions as Examples 1 to 3, except that it was not denatured with the denaturing agent presented in the above, through which the modified conjugated diene-based polymer according to an embodiment of the present invention is represented by Formula 1 By including the functional group derived from the denaturant, it can be confirmed that there is an effect of improving the processability, tensile properties, abrasion resistance and viscoelastic properties.

In addition, Example 1 exhibited an equivalent level of processability compared to Comparative Example 3, while the tensile properties, abrasion resistance, and viscoelastic properties were significantly improved, and Comparative Example 3 exhibited almost the same physical properties except for the processability of Comparative Example 2, which is an unmodified butadiene polymer. . At this time, Comparative Example 3 was used when the modifier material presented in the present invention was blended with a rubber composition, and these results were applied to the modifier represented by the formula (1) presented in the present invention as a modifier during polymer production, so that the functional group derived from the modifier in the polymer molecule It has the effect of improving the processability, tensile properties, abrasion resistance and viscoelastic properties by being introduced, and indicates that the above effects cannot be expressed when used as an additive such as a coupling agent when compounding the rubber composition.

Claims (12)

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

In Chemical Formula 1,
R ₁ and R ₃ are, independently of each other, a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or -COOR ₄ , wherein R ₄ is an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms,
R ₂ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
The method according to claim 1,
In Chemical Formula 1,
R ₁ and R ₃ are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl having 7 to 20 carbon atoms, and -COOR ₄ Is one,
The R ₄ is a modified conjugated diene polymer having 1 to 10 carbon atoms.
The method according to claim 1,
In Chemical Formula 1,
R ₁ and R ₃ are any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -COOR ₄ at the same time,
R ₂ is an alkylene group having 1 to 10 carbon atoms,
The R ₄ is a modified conjugated diene polymer having 1 to 10 carbon atoms.
The method according to claim 1,
The modified conjugate represented by Formula 1 is a modified conjugated diene polymer that 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 according to claim 1,
The polymer includes at least two main chains composed of a unit derived from a conjugated diene-based monomer,
The two main chains are modified conjugated diene-based polymers that are crosslinked by the action derived from the denaturant represented by Chemical Formula 1.
The method according to claim 1,
The polymer is a modified conjugated diene-based polymer containing a functional group derived from a modifier represented by Chemical Formula 1 in a side chain.
The method according to claim 1,
The polymer is a modified conjugated diene polymer having a weight average molecular weight of 200,000 g/mol to 1,500,000 g/mol.
1) polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent to prepare an active polymer; And
2) A method for preparing the modified conjugated diene-based polymer according to claim 1, comprising reacting the active polymer with a modifier represented by Chemical Formula 1:
[Formula 1]

In Chemical Formula 1,
R ₁ and R ₃ are, independently of each other, a monovalent hydrocarbon group having 1 to 20 carbon atoms; Or -COOR ₄ , wherein R ₄ is an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms,
R ₂ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
The method according to claim 8,
The catalyst composition is a method for producing a modified conjugated diene-based polymer that is used in an amount such that the neodymium compound is 0.02 mmol to 0.1 mmol based on 100 g of a conjugated diene-based monomer.
The method according to claim 8,
The neodymium compound is a method of preparing a modified conjugated diene-based polymer that is a compound represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R _a to R _c are, independently of each other, hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, not all R _a to R _c are hydrogen at the same time.
The method according to claim 8,
The denaturing agent is a method for producing a modified conjugated diene-based polymer, which is used in an amount of 0.1 to 10.0 parts by weight based on 100 parts by weight of the conjugated diene-based monomer.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 1.