KR20210052966A - Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer - Google Patents

Abstract

The present invention relates to a modifier useful for modifying a polymer as a compound represented by chemical formula 1, a modified conjugated diene-based polymer of a high molecular weight, a manufacturing method thereof, and a rubber composition comprising the same. The modified conjugated diene-based polymer, accordingly, has a high molecular weight because a main chain of the polymer constituting the polymer is cross-linked by a functional group derived from the modifier represented by the chemical formula 1, and therefore, has excellent mechanical properties such as tensile properties and abrasion resistance. In addition, with the functional group derived from the modifier introduced thereinto, the modified conjugated diene-based polymer can be applied to the rubber composition to have excellent processability and excellent compounding properties such as viscoelastic properties.

Description

Modifier, preparation method of modified conjugated diene polymer using the same, and modified conjugated diene polymer {Modifying agent, preparation method of modified conjugated diene polymer using the modifying agent and modified conjugated diene polymer}

The present invention relates to a modifier, a method for preparing a modified conjugated diene polymer using the same, and a modified conjugated diene polymer having a high molecular weight.

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 a filler 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 organolithium 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 neodymium compound as a method for enhancing the dispersibility of BR and a filler such as silica or carbon black, the living active end is modified with a specific modifier. Was 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 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, the living polymer obtained by coordination polymerization using the catalyst composition containing the neodymium compound _{is used as a coupling agent such as tin chloride (SnCl 4} ) to induce bonds between polymer chains constituting the polymer, thereby increasing the molecular weight to increase mechanical properties. A method of improvement has been studied, but the situation is limited due to the toxicity of the tin.

JP 5172663 B2

The present invention was conceived to solve the problems of the prior art, and by applying it to a conjugated diene-based polymer, it is possible to increase the molecular weight, suppress the intramolecular reaction of the polymer, and the intermolecular reaction (crosslinking reaction) is more predominantly modified. It is an object of the present invention to provide a modifier for rubber that can increase efficiency.

In addition, it is an object of the present invention to provide a modified conjugated diene-based polymer with improved mechanical properties such as tensile properties and abrasion resistance by having a high molecular weight, and improved blending properties such as viscoelastic properties by including a functional group derived from a modifier having a specific structure. It is done.

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 provides a denaturant represented by the following formula (1):

[Formula 1]

In Formula 1, R ₁ and R ₃ are each independently 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 alkylaryl group having 7 to 20 carbon atoms, and 7 to 20 carbon atoms. May be an arylalkyl group, a carboxyl group having 1 to 20 carbon atoms, or -COOR ₄ , wherein R ₄ may be an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, and R ₂ is substituted or unsubstituted with a substituent It may be a divalent hydrocarbon group having 3 to 30 carbon atoms containing one or more cyclic saturated hydrocarbons having 3 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 6 It may be one or more selected from the group consisting of 20 aryl groups.

In addition, the present invention 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 to R ₃ are as described above.

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 to R ₃ are as described above.

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

By applying the modifier according to the present invention to a conjugated diene-based polymer, the molecular weight can be increased, and mechanical properties such as tensile properties and abrasion resistance can be improved. In addition, by including the cyclic saturated hydrocarbon in the denaturing agent, the intramolecular reaction of the polymer is suppressed and the intermolecular reaction (crosslinking reaction) is more dominant than the linear-structured denaturing agent, thereby increasing the denaturation efficiency. As the denaturing efficiency is high, the amount of denaturant used can be reduced, and in particular, even if a small amount is used compared to the linear denaturing agent, the same level of denaturing efficiency can be secured.

In addition, the modified conjugated diene-based polymer according to the present invention may have a high molecular weight by crosslinking the polymer main chain constituting the polymer by a functional group derived from a modifier represented by Formula 1, and thus mechanical properties such as tensile properties and abrasion resistance. This can be excellent.

In addition, the modified conjugated diene-based polymer according to the present invention is applied to a rubber composition because the polymer chain is crosslinked by a functional group derived from a denaturant and a functional group derived from a modifier between the chains is introduced into the polymerization. This can be excellent.

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

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.

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, and an aryl group. It 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, a cycloalkyl-alkylene group, an unsaturated bond. It may represent a divalent atomic group in which carbon and hydrogen are bonded, such as an arylene group including one or more, 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).

The term'alkylene group' used in the present invention may mean a divalent saturated aliphatic 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, or the substance itself derived from a substance.

The present invention provides a modifier for rubber that can increase the molecular weight by applying it to a conjugated diene-based polymer, suppress the intramolecular reaction of the polymer, and increase the modification efficiency by more predominantly intermolecular reaction (crosslinking reaction) of the polymer.

Specifically, the denaturant according to an embodiment of the present invention is characterized in that it is represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ and R ₃ are each independently 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 alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and It may be a 1 to 20 carboxyl group or -COOR ₄ , wherein R ₄ may be a C 1 to C 20 alkyl group, or a C 3 to C 20 cycloalkyl group,

R ₂ may be a divalent hydrocarbon group having 3 to 30 carbon atoms containing one or more saturated or unsubstituted cyclic hydrocarbons having 3 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, It may be one or more selected from the group consisting of a 3 to 20 cycloalkyl group and a C 6 to C 20 aryl group.

Specifically, in Formula 1, R ₁ and R ₃ may each independently be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -COOR ₄ , and more specifically, R ₁ and R ₃ may be Each independently may be _{-COOR 4.}

When each of R ₁ and R ₃ is -COOR ₄ , R ₄ may be an alkyl group having 1 to 10 carbon atoms, and the alkyl group may include all linear or branched alkyl groups.

In addition, R ₁ and R ₃ may be 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, and more specifically _{, may be -COOR 4} at the same time, in which case R ₄ is the same I can.

In addition, in Formula 1, R ₂ may be a divalent hydrocarbon group having 6 to 30 carbon atoms including one or more saturated or unsubstituted cyclic saturated hydrocarbons having 6 to 12 carbon atoms, wherein the substituent is It may be one or more 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.

In addition, the _{cyclic saturated hydrocarbon having 6 to 12 carbon atoms contained in R 2} may be, for example, a cyclohexyl group, and R ₂ is 1 to 5, 1 to 3, or 1 to 5 of the cyclohexyl group. It may include two.

In addition, R ₂ may be an alkylene group having 7 to 30 carbon atoms including the cyclic saturated hydrocarbon, specifically, an alkylene group having 7 to 20 carbon atoms including the cyclic saturated hydrocarbon.

When R ₂ contains two or more cyclic saturated hydrocarbons, each of the cyclic saturated hydrocarbons may be linked to each other with an alkylene group having 1 to 5 carbon atoms, and when one cyclic saturated hydrocarbon is included, R ₂ is cyclic The saturated hydrocarbon and the alkylene group of may be sequentially connected. In addition, the _{cyclic saturated hydrocarbon contained in R 2} may be directly connected to -NH- of Formula 1.

In addition, the substituent may be specifically an alkyl group having 1 to 10 carbon atoms, more specifically an alkyl group having 1 to 5 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 includes an amide group on both sides of a divalent hydrocarbon group including a cyclic saturated hydrocarbon; Azo group; And a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or an ester group is sequentially bonded, wherein the azo group exhibits high reactivity with the double bond present in the polymer chain constituting the polymer. 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-based polymer to improve mechanical properties such as tensile properties and wear resistance.

In addition, the modifier according to an embodiment of the present invention may include a functional group derived from a denaturant between polymer chains while inducing crosslinking between polymer chains by an azo group, such as a divalent hydrocarbon group including a cyclic saturated hydrocarbon; Amide group; And by introducing a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group or an ester group, the polymer may be modified, and the aliphatic and/or aromatic hydrocarbon group may increase the affinity for the polymerization solvent to increase the solubility of the modifying agent and modify it. The reaction can be made easily. In addition, the ester group can improve the stability of the denaturant by reducing the electron density of the azo group.

That is, the modifier according to an embodiment of the present invention may be one that acts as a crosslinking agent for crosslinking the polymer chain by including two azo groups, and at the same time acts as a modifier for modifying the physical properties of the polymer by introducing a functional group into the polymer chain.

In addition, in an embodiment of the present invention, other modifiers contain cyclic saturated hydrocarbons between azo groups, so that when applied to a polymer, reactions within the polymer chain are suppressed and interchain reactions are more dominant compared to structures containing only divalent linear hydrocarbon groups. It can be, and accordingly, the coupling and modification efficiency can be more excellent.

The present invention provides a modified conjugated diene polymer having high molecular weight and excellent mechanical properties such as tensile properties and abrasion resistance, and excellent blending 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 denaturant represented by the following formula (1).

[Formula 1]

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

In addition, the denaturant of the functional group derived from the denaturant may be the same as the above-described denaturant.

More specifically, in the modified conjugated diene-based polymer according to an embodiment of the present invention, the polymer comprises a polymer chain including 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 a denaturant shown.

Specifically, it will be described through the following Chemical Formula 2.

[Formula 2]

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

In general, 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 units derived from conjugated diene-based monomers.

Specifically, the modifier represented by Formula 1 according to an embodiment of the present invention is a material having a structure in which an azo group is bonded to both sides around a hydrocarbon group containing a cyclic saturated hydrocarbon, and the azo group in the modifier is a conjugated diene group. It is possible to exhibit high reactivity with a double bond in the polymer chain composed of a monomer-derived unit, and thus each azo group in the modifier and two polymer chains react respectively, so that the two polymer chains are crosslinked with a functional group derived from the denaturant. It is possible to form a polymer chain unit represented by Chemical Formula 2.

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 form 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 Formula 1 in the side chain of the polymer. Specifically, as identified in the polymer chain unit represented by Formula 2, in the present invention, the functional group derived from the modifier exists between the polymer chains and serves as a crosslinking role to link the polymer chains. It may be bound to.

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 include 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 may be used.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a lanthanum-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 moiety 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/ mol, and when applied to a rubber composition within this range, it has excellent tensile properties and excellent processability, so kneading is easy due to the improved workability of the rubber composition, and the mechanical properties and physical property balance of the rubber composition are excellent. . The weight average molecular weight may specifically be 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, 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 (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 a common average of the molecular weights of individual polymers calculated by measuring the molecular weights of n polymer chains and dividing by n by obtaining the sum of these molecular weights, 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).

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 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, and specifically 30 or more and 80 or less or 35 or more and 75 or less. I can. 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 under conditions of 100° C. and Rotor Speed 2±0.02 rpm using a Mooney viscometer, for example, a Large Rotor of Monsanto's MV2000E. Specifically, 37.3 parts by weight of TDAE (treated distillate aromatic extracted) oil, which is a process oil, is added to the polymer, and 37.3 parts by weight of the polymer is added to the polymer. The Mooney viscosity was measured while filling the cavity and applying torque by operating a platen.

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.

Here, the cis-1,4 bond content and vinyl content in the polymer by Fourier transform infrared spectroscopy (FT-IR) are a conjugated diene-based polymer 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 around 1130 cm -1} of the measurement spectrum (a, baseline), the minimum peak around ^{967 cm -1 representing the trans-1,4 bond} Using the value (b), the minimum peak value around ^{911 cm -1 representing vinyl bonds (c), and the minimum peak value around 736 cm -1} representing cis-1,4 bonds (d), determine the respective contents. I saved it.

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 ₃ 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 including the organometallic moiety, the organometallic moiety may be an activated organometallic moiety at the end of the conjugated diene-based polymer (activated organometallic moiety at the molecular chain end), among which anionic polymerization or When the activated organometallic portion of the conjugated diene-based polymer is obtained by coordination anionic polymerization, the organometallic portion may represent an activated organometallic portion of the terminal.

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 0.02 mmol to 1.0 mmol based on a total of 100 g of a conjugated diene-based monomer, and specifically, the neodymium compound is based on a total of 100 g of a conjugated diene-based monomer. It may be used in an amount of 0.1 mmol to 0.5 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); Xanthogenate (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 compound containing at least one rare earth element-carbon bond (e.g., Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn (cyclooctatetraene), (C ₅ Me ₅ ) ₂ LnR , LnR ₃ , Ln (allyl) ₃ , or Ln (allyl) ₂ Cl, and the like, wherein Ln is a rare earth metal element, R is a hydrocarbyl group), and the like, and any one or a mixture of two or more thereof Can include.

Specifically, the neodymium compound may include a neodymium 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, but may be a neodymium-based compound.

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 period of 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 rare earth 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 generally used as an alkylating agent in the manufacture 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-octyl aluminum 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, 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, 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 addition of the catalyst composition, 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 containing a functional group by modifying 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 end of the polymer 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. Thus, a modified conjugated diene-based polymer having a structure in which the functional group derived from the modifier exists as a linking group connecting the polymer chains and the functional group derived from the modifying agent is bonded to the side chain of the polymer chain can be prepared.

[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.

The modifier 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 modifier may be used in an amount of 1 to 5 parts by weight based on 100 parts by weight of the conjugated diene-based monomer.

In addition, 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 to 15 moles relative to 1 mole 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 polymer in an amount of 0.1 wt% or more and 100 wt% or less, specifically 10 wt% to 100 wt%, and more specifically 20 wt% to 90 wt%. 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-based 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, the processability of the rubber composition may be deteriorated, and when it is less than 80 cc/100 g, the reinforcing performance by 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, examples, etc. will be described in detail to aid understanding of the present invention. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the following examples. Embodiments of the present invention are provided to more completely describe the present invention to those with average knowledge in the field to which the present invention belongs.

Example

Manufacturing Example 1

In an ice bath, add 10 g of 4,4-methylenebis(cyclohexyl isocyanate)(4,4-methylenebis(cyclohexyl isocyanate)) to a 50 ml round bottom flask, add acetonitrile, and 7.9 g of ethyl carbazate. It reacted while slowly adding dropwise. When the reaction was completed, a white solid was obtained through a filter.

Into a 100 ml round bottom flask, 18 g of the white solid is added, _{40 ml of dichloromethane (CH 2} Cl ₂ ) is added, and 6.6 g of pyridine is added dropwise to dissolve the solid, and 13.6 g of N-bromosuccinimide is slowly added dropwise in an ice bath. While reacting. When the reaction was completed, it was dissolved in dichloromethane, extracted with water, separated and purified to obtain 14 g of a denaturant represented by the following formula 1-1 as a red liquid (yield 78%). ^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 ) 9.0 (2H, d), 4.45 (4H, m), 3.8 (1H, s), 3.49 (1H, m), 1.87-0.88 (22H, m)

Manufacturing Example 2

In an ice bath, 100 g of hydrazine monohydrate was added to a 500 ml round bottom flask, 125 ml of acetonitrile was added, and 98 ml of 2-ehtylhexyl chloroformate was slowly added dropwise. While reacting. Thereafter, the solvent was removed using a rotary evaporator, dissolved in diethyl ether, _{extracted with an aqueous NaHCO 3} solution, separated and purified to obtain a pink solution.

5 g of 4,4-methylenebis (cyclohexyl isocyanate) (4,4-methylenebis (cyclohexyl isocyanate)) was added to a 50 ml round bottom flask, acetonitrile was added, and 10.8 g of the pink solution was slowly added dropwise to react. When the reaction was completed, 7.4 g of a white solid was obtained through filtration in a 60% yield.

In a 50 ml round bottom flask, 7.4 g of the white solid was added, _{30 ml of dichloromethane (CH 2} Cl ₂ ) was added, and 2.0 g of pyridine was added dropwise to dissolve the solid, and 4.1 g of N-bromosuccinimide was slowly added dropwise in an ice bath. While reacting. Thereafter, by dissolving in dichloromethane, extraction with water, separation and purification, 5 g of a denaturant represented by the following formula 1-2 as a red liquid was obtained (yield 68%). ^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 ) 9.0 (2H, d), 4.45 (4H, m), 3.9 (1H, m), 3.0 (2H, m), 1.6 (2h, m), 1.33 (6H , t), 1.33-1.13(4H, m), 1.13(6H, m), 1.12-0.88(5H, m)

Manufacturing Example 3

In an ice bath, 10 g of isophorone diisocyanate was added to a 50 ml round bottom flask, acetonitrile was added, and 9.4 g of ethyl carbazate was slowly added dropwise to react. When the reaction was completed, a white solid was obtained through a filter.

In a 100 ml round bottom flask, 18 g of the white solid was added, _{56 ml of dichloromethane (CH 2} Cl ₂ ) was added, and 7.8 g of pyridine was added dropwise to dissolve the solid, and 16 g of N-bromosuccinimide was slowly added dropwise in an ice bath. While reacting. Upon completion of the reaction, 16 g of a denaturant represented by the following formula 1-3 as a red liquid was obtained by extraction with water in dichloromethane, separation and purification (yield 83%). ^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 ) 9.0 (2H, d), 4.45 (4H, m), 3.9 (1H, m), 3.0 (2H, m), 1.6 (2H, m), 1.33 (6H , t), 1.33-1.13(4H, m), 1.13(6H, m), 1.12-0.88(5H, m)

Example 1

After adding 800 g of 1,3-butadiene and 5.4 kg of n-hexane to 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 30 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 versatate:DIBAH:DEAC=1:16:2.4 molar ratio, followed by mixing to prepare. After adding 3.0 mmol of the denaturant of Formula 1-1 prepared in Preparation Example 1, the denaturation reaction was performed at 70°C for 30 minutes. 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 1-2 was used instead of the modifier of Formula 1-1.

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 1-3 was used instead of the modifier of Formula 1-1.

Comparative Example 1

As an unmodified butadiene polymer, CB29 (Lanxess Co., Ltd.) 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 20L 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 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 versatate:DIBAH:DEAC=1:16:2.4 molar ratio, 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

After adding 800 g of 1,3-butadiene and 5.4 kg of n-hexane to 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 30 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 versatate:DIBAH:DEAC=1:16:2.4 molar ratio, followed by mixing to prepare. After adding 3.0 mmol of the following compound as a denaturing agent, the denaturation reaction was performed at 70° C. for 30 minutes. 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.

Comparative Example 4

A modified butadiene polymer was prepared in the same manner as in Comparative Example 3, except that 6.5 mmol of the same modifier was used in Comparative Example 3.

Experimental Example 1

For the polymers of Examples 1 to 3 and Comparative Examples 1 to 4, physical properties 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 the condition of 40° C., and then loaded and flowed through gel permeation chromatography (GPC). At this time, the column was used in combination with two PLgel Olexis columns and one PLgel mixed-C column manufactured by Polymer Laboratories. In addition, all newly replaced columns used mixed bed type columns, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

2) Mooney viscosity (RP)

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 at this time was allowed to stand at room temperature (23±3°C) for at least 30 minutes, and then 27±3g was collected and filled into the die cavity, and the Mooney viscosity was measured while applying a torque by operating a platen.

division Example Comparative example One 2 3 One 2 3 4 GPC results Mn (x10 ³ g/mol) 330.0 351.7 362.6 331.8 284.2 290.3 320.1 Mw (x10 ³ g/mol) 800.3 814.7 798.2 884.5 671.6 701.6 821.4 Mp(x10 ³ g/mol) 611.0 591.9 601.8 604.1 490.5 550.8 619.8 MWD 2.42 2.32 2.20 2.67 2.36 2.42 2.57 Mooney viscosity (RP, ML1+4, @100℃)(MU) 42.0 40.0 41.5 39.9 43.1 40.0 35.0

As shown in Table 1, the polymers of Examples 1 to 3 increased the weight average molecular weight and the number average molecular weight compared to the polymer of Comparative Example 2, except that the polymer of Comparative Example 2 did not undergo a denaturation reaction. It was prepared through the same method as in Examples 1 to 3. This increase in molecular weight is a result of indicating that the polymers of Examples 1 to 3 are crosslinked by the functional groups derived from the modifying agent and the functional groups derived from the modifying agent are introduced.

In addition, Examples 1 to 3 can be confirmed that the weight average molecular weight and number average molecular weight increased even compared to Comparative Example 3 in which the same amount of the linear modifier was applied to Examples 1 to 3, and when the same amount of the modifier was applied, Comparative Example It can be seen that the denaturants of Examples 1 to 3 can have a higher denaturation rate compared to the denaturant of 3.

Experimental Example 2

After preparing a rubber composition and a rubber specimen using the polymers of Examples 1 to 3 and Comparative Examples 1 to 4, Mooney viscosity, tensile stress, 300% modulus, abrasion resistance, and viscoelastic properties were measured by the following methods. . The results are shown in Table 2 below.

(1) Preparation of rubber composition and rubber specimen

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 blending 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 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. This resulted in a vulcanized formulation in sheet form. 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 allowed to stand at room temperature (23±3℃) for at least 30 minutes, then collect 27±3g, fill it inside the die cavity, operate the platen, and measure the Mooney viscosity (FMB) while applying torque. 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 strength, tensile stress and 300% modulus

After vulcanizing each of the rubber compositions at 150° C. for t90 minutes, the tensile strength, tensile stress, and modulus at 300% elongation (M-300%) of the vulcanized material 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 indes: 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 indicates less road surface resistance, and the Tanδ value at 60°C indicates rotational resistance characteristics (fuel economy).

division Example Comparative example One 2 3 One 2 3 4 Mooney viscosity (FMB) 79 75 80 78 76 79 77 △MV 37.0 35.0 38.5 38.1 43.1 39.0 39.8 Tensile properties
(Index, %) M-300% 105 104 110 100 95 100 102 The tensile strength 106 108 109 100 97 102 103 Wear resistance (Index, %) 110 112 115 100 95 102 107 Viscoelastic properties
(Index, %) Tanδ @ 0℃ 102 103 101 100 98 99 103 Tanδ @ 60℃ 103 101 100 100 99 100 102

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

[Equation 1]

Index=(measured value/reference value)×100

[Equation 2]

Index=(reference value/measured value)×100

As shown in Table 2, it can be seen that Examples 1 to 3 have excellent workability equal to or higher than Comparative Examples 1 to 4, while both tensile properties, abrasion resistance, and viscoelastic properties are greatly excellent.

Specifically, Examples 1 to 3 significantly improved tensile properties, abrasion resistance, and viscoelastic properties while having improved processability compared to Comparative Examples 1 and 2, wherein Comparative Example 2 was not modified with the modifier presented in the present invention. Unmodified butadiene polymer prepared under the same conditions as in Examples 1 to 3, except that the modified conjugated diene polymer according to an embodiment of the present invention is processed by including a functional group derived from a denaturant represented by Formula 1 , It can be seen that the tensile properties, abrasion resistance, and viscoelastic properties are improved.

In addition, Examples 1 to 3 showed excellent workability compared to Comparative Example 3, while the tensile properties, abrasion resistance, and viscoelastic properties were significantly improved, and from this, the modifier having a linear structure outside the scope of the present invention is an embodiment of the present invention even though the functional groups are similar. It can be seen that the denaturing efficiency is significantly lower than that of the modifier according to the example, and in addition, Examples 1 to 3 have excellent processability and tensile properties compared to Comparative Example 4 in which the same modifier as in Comparative Example 3 was applied in an excessive amount compared to the amount used in Examples. , Abrasion resistance and viscoelastic properties were greatly improved.

Claims (12)

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

In Formula 1,
R ₁ and R ₃ are each independently 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 alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and 1 to 20 carboxyl group or -COOR ₄ , wherein R ₄ is a C 1 to C 20 alkyl group, or a C 3 to C 20 cycloalkyl group,
R ₂ is a C 3 to C 30 divalent hydrocarbon group containing at least one C 3 to C 20 cyclic saturated hydrocarbon substituted or unsubstituted with a substituent, wherein the substituent is a C 1 to C 20 alkyl group, C 3 It is one or more selected from the group consisting of a cycloalkyl group of to 20 and an aryl group having 6 to 20 carbon atoms.
The method of claim 1,
In Formula 1,
R ₁ and R ₃ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -COOR ₄ , wherein R ₄ is an alkyl group having 1 to 10 carbon atoms,
R ₂ is a modifying agent which is a divalent hydrocarbon group having 6 to 30 carbon atoms containing at least one saturated cyclic hydrocarbon having 6 to 12 carbon atoms unsubstituted or substituted with a substituent.
The method of claim 1,
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]

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 ₃ are each independently 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 alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and 1 to 20 carboxyl group or -COOR ₄ , wherein R ₄ is a C 1 to C 20 alkyl group, or a C 3 to C 20 cycloalkyl group,
R ₂ is a C 3 to C 30 divalent hydrocarbon group containing at least one C 3 to C 20 cyclic saturated hydrocarbon substituted or unsubstituted with a substituent, wherein the substituent is a C 1 to C 20 alkyl group, C 3 It is one or more selected from the group consisting of a cycloalkyl group of to 20 and an aryl group having 6 to 20 carbon atoms.
The method of claim 4,
The polymer includes at least two main chains composed of units derived from conjugated diene-based monomers,
The two main chains are modified conjugated diene-based polymers that are crosslinked by a functional group derived from a denaturant represented by Formula 1.
The method of claim 4,
The polymer is a modified conjugated diene-based polymer containing a functional group derived from a modifier represented by Formula 1 in the side chain.
The method of claim 4,
The polymer has a weight average molecular weight of 200,000 g/mol to 1,500,000 g/mol,
A modified conjugated diene-based polymer having a number average molecular weight of 50,000 g/mol to 1,000,000 g/mol.
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 of preparing a modified conjugated diene-based polymer comprising reacting the active polymer with a denaturant represented by Formula 1:
[Formula 1]

In Formula 1,
R ₁ and R ₃ are each independently 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 alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and 1 to 20 carboxyl group or -COOR ₄ , wherein R ₄ is a C 1 to C 20 alkyl group, or a C 3 to C 20 cycloalkyl group,
R ₂ is a C 3 to C 30 divalent hydrocarbon group containing at least one C 3 to C 20 cyclic saturated hydrocarbon substituted or unsubstituted with a substituent, wherein the substituent is a C 1 to C 20 alkyl group, C 3 It is one or more selected from the group consisting of a cycloalkyl group of to 20 and an aryl group having 6 to 20 carbon atoms.
The method of 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 of claim 8,
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 8,
The method for producing a modified conjugated diene-based polymer is used in an amount of 0.1 parts by weight 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 polymer according to any one of claims 4 to 7.