KR102595111B1 - 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 polymer, a method for producing the same, and a rubber composition containing the same. The resulting modified conjugated diene polymer can have a high molecular weight because the polymer main chain constituting the polymer is crosslinked by a functional group derived from the denaturant represented by Chemical Formula 1, and thus can have excellent mechanical properties such as tensile properties and wear resistance. In addition, by introducing a functional group derived from a denaturant, it can be applied to a rubber composition and have excellent processability and excellent compounding properties such as viscoelastic properties.

Description

Modified conjugated diene polymer, preparation method thereof and rubber composition comprising the same}

The present invention relates to a high molecular weight modified conjugated diene polymer, a method for producing the same, and a rubber composition containing the same.

Recently, in response to the demand for lower fuel consumption for automobiles, conjugated diene-based polymers are required as rubber materials for tires, which have low running resistance, excellent abrasion resistance and tensile properties, and also have steering stability as represented by wet skid resistance.

In order to reduce the running resistance of a tire, there is a way to reduce the hysteresis loss of vulcanized rubber, and the rebound elasticity of 50°C to 80°C, tan δ, and Goodrich heat generation are used as evaluation indicators for vulcanized rubber. That is, a rubber material with high rebound elasticity at the above temperature or low tan δ or Goodrich heat generation is preferable.

Natural rubber, polyisoprene rubber, and polybutadiene rubber are known as rubber materials with low hysteresis loss, but these have the 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 are used as tire rubber. .

When the BR or SBR above is used as a rubber material for tires, it is usually blended with fillers such as silica or carbon black to obtain the required physical properties of the tire. However, since the affinity between the BR or SBR and the filler is not good, there is a problem in that physical properties including wear resistance, crack resistance, or processability are lowered.

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

In addition, as a method to increase the dispersibility of BR and fillers such as silica or carbon black, in the living polymer obtained by coordination polymerization using a catalyst composition containing a neodymium compound, a method of modifying the living active end with a specific denaturant This was developed. However, in the case of polymers with modified ends, the affinity for fillers is improved, which has the advantage of improved blending properties, such as tensile properties and viscoelastic properties, but on the other hand, blending processability is greatly reduced, resulting in poor processability.

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

JP 5172663 B2

The present invention was developed to solve the problems of the prior art, and is a modified conjugate with improved mechanical properties such as tensile properties and wear resistance by having a high molecular weight, and improved compounding properties such as viscoelastic properties by including functional groups derived from the modifier. The purpose is to provide a diene-based polymer.

Additionally, the present invention aims to provide a method for producing the above-described modified conjugated diene polymer.

In addition, the present invention aims to provide a rubber composition containing the modified conjugated diene polymer.

In order to solve the above problems, the present invention provides 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 a monovalent hydrocarbon group having 1 to 20 carbon atoms; or -COOR ₄ , where R ₄ is an alkyl group with 1 to 10 carbon atoms, or a cycloalkyl group with 3 to 10 carbon atoms, and R ₂ is an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, and a cycloalkyl group with 6 to 20 carbon atoms. It is a divalent hydrocarbon group having 1 to 20 carbon atoms that is unsubstituted or substituted with one or more substituents selected from the group consisting of aryl groups.

In addition, the present invention includes the steps of preparing an active polymer by polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition containing a neodymium compound (step 1); and reacting the active polymer with a modifier represented by Formula 1 (step 2). A method for producing the modified conjugated diene-based polymer is provided:

[Formula 1]

In Formula 1,

R ₁ and R ₃ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms; or -COOR ₄ , where R ₄ is an alkyl group with 1 to 10 carbon atoms, or a cycloalkyl group with 3 to 10 carbon atoms, and R ₂ is an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, and a cycloalkyl group with 6 to 20 carbon atoms. It is a divalent hydrocarbon group having 1 to 20 carbon atoms that 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 containing the modified conjugated diene polymer.

The modified conjugated diene polymer according to the present invention can have a high molecular weight because the polymer main chain constituting the polymer is crosslinked by a functional group derived from the denaturant represented by Chemical Formula 1, and thus has excellent mechanical properties such as tensile properties and wear resistance. can do.

In addition, the modified conjugated diene polymer according to the present invention has polymer chains crosslinked by functional groups derived from the denaturing agent and at the same time functional groups derived from the denaturing agent are introduced between the chains during polymerization, so that it can be applied to rubber compositions and has excellent processability and compound properties such as viscoelastic properties. This can be excellent.

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

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

Terms or words used in this specification and claims should not be construed as limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.

The term 'substitution' used in the present invention may mean that the hydrogen of a functional group, atomic group, or compound is replaced with a specific substituent. When the hydrogen of a functional group, atomic group, or compound is replaced with a specific substituent, it exists in the functional group, atomic group, or compound. Depending on the number of hydrogens, one or two or more substituents may be present. Additionally, when a plurality of substituents are present, each substituent may be the same or different from each other.

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

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

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

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 refer to a cyclic aromatic hydrocarbon, and may also refer to a monocyclic aromatic hydrocarbon with one ring formed or a polycyclic aromatic hydrocarbon with two or more rings bonded together. It may mean including all aromatic hydrocarbons.

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 or structure derived from a certain substance, or the substance itself.

The present invention provides a modified conjugated diene-based polymer that has excellent mechanical properties such as tensile properties and wear resistance by having a high molecular weight, and has excellent compounding properties such as viscoelastic properties by containing functional groups derived from a modifier.

Specifically, the modified conjugated diene-based polymer according to an embodiment of the present invention is characterized by including 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 a monovalent hydrocarbon group having 1 to 20 carbon atoms; or -COOR ₄ , where R ₄ is an alkyl group with 1 to 10 carbon atoms, or a cycloalkyl group with 3 to 10 carbon atoms, and R ₂ is an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, and a cycloalkyl group with 6 to 20 carbon atoms. It is a divalent hydrocarbon group having 1 to 20 carbon atoms that is unsubstituted or substituted with one or more substituents selected from the group consisting of aryl groups.

The denaturant according to the present invention may be the compound represented by Formula 1, or may contain another compound capable of denaturing the conjugated diene polymer together with the compound represented by 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 it may be -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 an arylalkyl group having 7 to 20 carbon atoms. Specifically, R ₁ and R ₃ are each an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 12 carbon atoms, and an aryl group with 6 to 12 carbon atoms. and an arylalkyl group having 7 to 12 carbon atoms.

In addition, when R ₁ and R ₃ are each -COOR ₄ , where R ₄ may be an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, specifically, R ₄ is an alkyl group having 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 Formula 1, R ₂ is substituted or unsubstituted with one or more substituents selected from the group consisting of an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, and an aryl group with 6 to 20 carbon atoms. 2 may be a 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, ethylene group, or propylene group; Arylene groups having 6 to 20 carbon atoms, such as phenylene groups; Or, a combination thereof 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 with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, and an aryl group with 6 to 20 carbon atoms, R ₂ has 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 simultaneously 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 , where In R ₄ may be 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 denaturant 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 denaturant according to an embodiment of the present invention includes a nitroxyl group on both sides of an aliphatic hydrocarbon group; azo group; and has a structure in which a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or an ester group are sequentially bonded, and the azo group exhibits high reactivity with the double bond present in the polymer chain constituting the polymer, thereby forming the two azo groups in the denaturant. can react with the double bonds of each polymer chain to crosslink two polymer chains, thereby improving the molecular weight of the modified conjugated diene polymer and improving mechanical properties such as tensile properties and wear resistance.

In addition, the denaturant according to an embodiment of the present invention induces crosslinking between polymer chains by an azo group and contains functional groups derived from the denaturant between polymer chains, such as a divalent aliphatic hydrocarbon group; nitroxyl group; And the polymer can be modified by introducing a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or an ester group. The aliphatic and aromatic hydrocarbon groups can increase the affinity for the polymerization solvent and increase the solubility of the modifier, thereby causing a modification reaction. It can be done easily. Additionally, the ester group can improve the stability of the denaturant by reducing the electron density of the azo group.

In other words, the denaturant according to one embodiment of the present invention may function as a crosslinking agent that crosslinks the polymer chain by containing two azo groups and at the same time act as a denaturant that modifies the physical properties of the polymer by introducing a functional group 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 containing at least two conjugated diene-based monomer-derived units, and the two polymer chains are represented by Formula 1: It may be cross-linked by the functional group derived from the indicated denaturant.

Specifically, it is explained through Chemical Formula 2 below.

[Formula 2]

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

Typically, a polymer is an aggregate of polymer chains composed of linked 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 denaturant represented by Formula 1 according to an embodiment of the present invention is a material with an azo group bonded to both sides of an aliphatic hydrocarbon group, and the azo group in the denaturant is composed of a unit derived from a conjugated diene monomer. The polymer represented by Formula 2 can exhibit high reactivity with double bonds in the polymer chain, and the two polymer chains are cross-linked with the functional group derived from the denaturant interposed by each azo group in the denaturant reacting with each of the two polymer chains. 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 all polymer chains constituting the polymer have a structure represented by Formula 2. It may be forming a polymer chain unit.

Additionally, the modified conjugated diene-based polymer according to an embodiment of the present invention may include a functional group derived from a denaturant represented by Formula 1 in the polymer side chain. Specifically, as can be seen from the polymer chain unit represented by Formula 2, in the present invention, the functional group derived from the denaturant is present between polymer chains and serves as a bridge connecting the polymer chains, and is a side chain rather than the end of the polymer chain. It may be connected to .

Additionally, 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 monomer, and 20% by weight or less of units derived from other conjugated diene-based monomers that can optionally be copolymerized with 1,3-butadiene. There is an effect that the 1,4-cis bond content in the polymer is not reduced within the above range. At this time, the 1,3-butadiene monomer includes 1,3-butadiene or its derivatives such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. Other conjugated diene monomers that can be copolymerized with 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, or 2,4-hexadiene, etc., and any one or two or more of these compounds may be used.

Additionally, 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 containing 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. It can be mol, and within this range, when applied to a rubber composition, the tensile properties are excellent and the processability is excellent, which makes mixing kneading easier due to improved workability of the rubber composition, resulting in excellent mechanical properties and physical property balance of the rubber composition. . 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 may be, for example, 100,000 g/mol to 800,000 g/mol, or 200,000 g. /mol to 500,000 g/mol.

Additionally, 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 polymer can be calculated from the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). At this time, the number average molecular weight (Mn) is the common average of the individual polymer molecular weights calculated by measuring the molecular weight of n polymer chains, calculating the total of these molecular weights, and dividing by n, and the weight average molecular weight (Mw) is the polymer Indicates 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 refer to polystyrene conversion molecular weight 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 weight average molecular weight (Mw) and number average molecular weight conditions along with the molecular weight distribution described above, it is applied to a rubber composition. It has excellent tensile properties, viscoelasticity, and processability, and has an excellent balance of physical properties between them.

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. You can. The modified conjugated diene-based polymer according to the present invention may have excellent processability by having a Mooney viscosity in the above-mentioned range.

In the present invention, the Mooney viscosity was measured using a Mooney viscometer, for example, a large rotor of Monsanto's MV2000E, at 100°C and a rotor speed of 2±0.02 rpm. Specifically, 37.3 parts by weight of treated distillate aromatic extracted (TDAE) oil, which is a process oil, was added to the polymer and mixed, and left at room temperature (23 ± 5°C) for more than 30 minutes, then 27 ± 3 g was collected and die. Mooney viscosity was measured by filling the cavity and operating the platen to apply torque.

Additionally, 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, the wear resistance, crack resistance, and ozone resistance of the rubber composition can be improved.

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

Here, the cis-1,4 bond content and vinyl content in the polymer by Fourier transform infrared spectroscopy (FT-IR) are obtained from the 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 a carbon disulfide solution, the maximum peak value (a, baseline) around 1130 cm ^-1 of the measured spectrum, and the minimum peak around 967 cm ^-1 indicating trans-1,4 bond. Each content was calculated using the value (b), the minimum peak value (c) around 911 cm ^-1 indicating a vinyl bond, and the minimum peak value (d) around 736 cm ^-1 indicating a cis-1,4 bond. It was saved.

Additionally, the present invention provides a method for producing the above modified conjugated diene polymer.

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

[Formula 1]

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

Step 1 is a step of preparing an active polymer containing an organometallic moiety by polymerizing a conjugated diene monomer, and can be performed by polymerizing the conjugated diene monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent.

In the present invention, the organometallic moiety in the active polymer containing the organometallic moiety may be an activated organometallic moiety at the end of the conjugated diene polymer (activated organometallic moiety at the end of the molecular chain), and among these, anionic polymerization or When the activated organometallic moiety of the conjugated diene polymer is obtained through coordination anionic polymerization, the organometallic moiety may represent a terminal activated organometallic moiety.

The conjugated diene 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 -1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene, etc. It may be one or more types 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 a total of 100 g of conjugated diene monomers. Specifically, the neodymium compound may be used in an amount of 0.02 mmol to 1.0 mmol based on a total of 100 g of conjugated diene monomers. 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 compounds include their carboxylate salts (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, etc.); 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 (e.g. neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate, etc.); dithiocarbamate (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate, or neodymium dibutyldithiocarbamate, etc.); xanthogenates (e.g., neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl xanthogenate, or neodymium benzyl xanthogenate, etc.); β-diketonates (e.g. neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl acetonate, etc.); Alkoxides or allyloxides (e.g. neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.); Halides or pseudohalides (such as neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); Oxyhalides (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide, 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), any one of these, or a mixture of two or more thereof. It can be included.

Specifically, the neodymium compound may include a neodymium compound represented by the following formula (3).

[Formula 3]

In Formula 3, R _a to R _c are independently hydrogen or an alkyl group having 1 to 12 carbon atoms, but 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 one species.

In addition, as another example, considering the excellent solubility in solvents without concerns about oligomerization, the conversion rate to catalytically active species, and the resulting excellent effect of improving catalytic activity, the neodymium compound is more specifically, in Formula 3, R _a is 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, but R _b and R _c may be neodymium-based compounds that are not hydrogen at the same time.

As 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 At the same time, it may not be hydrogen, and specific examples 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 It may be one or more selected from the group consisting of hexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ , and Nd (2-ethyl-2-hexyl nonanoate) ₃ , among which the above Neodymium-based compounds include Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2, It may be one or more selected from the group consisting of 2-dihexyl decanoate) ₃ , and Nd (2,2-dioctyl decanoate) ₃ .

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.

In this way, the neodymium-based compound represented by Formula 3 includes a carboxylate ligand containing an alkyl group of various lengths of 2 or more carbon atoms at the α (alpha) position as a substituent, thereby inducing a steric change around the neodymium center metal to form a compound. It can block liver aggregation, and thus has the effect of suppressing oligomerization. In addition, such neodymium-based compounds have high solubility in solvents and have the effect of increasing the conversion rate to catalytically active species by reducing the proportion of neodymium located in the central portion where conversion to catalytically active species is difficult.

Additionally, 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 non-polar solvent at room temperature (25°C).

In the present invention, the solubility of a neodymium-based compound refers to the degree to which it dissolves clearly without clouding, and by exhibiting such high solubility, it can exhibit excellent catalytic activity.

Additionally, 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 the effect of improving the solubility of the neodymium compound in the solvent by using a 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 an amount of 30 moles or less, or 1 to 10 moles per mole of 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 monovalent or divalent alcohol.

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

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

Hereinafter, the (a) alkylating agent, (b) halide, and (c) conjugated diene monomer will be separately 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 commonly used as an alkylating agent in the production of diene polymers, and is soluble in the polymerization solvent, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound, and forms a metal-carbon bond. It may be an organometallic compound containing.

Specifically, the organic aluminum compounds include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, and tripentyl. Alkyl aluminum such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; Diethylaluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum 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-butylaluminum hydride. hydride, phenyl isobutylaluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropyl 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 hydrides such as -n-butyl aluminum hydride, benzylisobutyl aluminum hydride, or benzyl-n-octyl aluminum hydride; Hydrocarbylaluminum 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. can be mentioned. The organic magnesium compounds include alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or dibenzyl magnesium, and the like. Examples of the organic lithium compound include alkyl lithium compounds such as n-butyllithium.

Additionally, the organoaluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting water with a trihydrocarbyl aluminum compound. Specifically, it may be a straight-chain aluminoxane of the formula 4a below or a cyclic aluminoxane of the formula 4b below.

[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 from 2 to 50.

More specifically, the aluminoxane is methylaluminoxane (MAO), modified methylaluminoxane (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- It may be dimethylphenyl aluminoxane, etc., and any one or a mixture of two or more of these may be used.

In addition, the modified methylaluminoxane is obtained by replacing the methyl group of methylaluminoxane with a modification group (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 independently integers of 2 or more. Additionally, in Formula 5, Me represents a methyl group.

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

More specifically, the modified methylaluminoxane may be one in which about 50 mol% to 90 mol% of the methyl group of methylaluminoxane is replaced with the hydrocarbon group described above. When the content of substituted hydrocarbon groups in modified methylaluminoxane is within the above range, alkylation can be promoted and catalytic activity can be increased.

Such modified methylaluminoxane can be manufactured according to conventional methods, and specifically, it can be manufactured 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 these may be used.

In addition, the catalyst composition according to an embodiment of the present invention may include the alkylating agent at a molar ratio of 1 to 200, specifically 1 to 100 molar ratio, and more specifically 3 to 20 molar ratio with respect to 1 mole of the neodymium compound. there is. If the alkylating agent is included in a molar ratio exceeding 200, it is not easy to control the catalytic reaction during polymer production, and there is a risk that an excessive amount of alkylating agent may cause side reactions.

(b) Halides

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

The halogen group may include fluorine, chlorine, bromine, or iodine.

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

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

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

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 ), and silicon tetrabromide. , arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide or selenium tetraiodide, etc. can be mentioned.

In addition, the metal halide includes 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 diiodide, tetraiodide Examples include germanium, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

In addition, the organometallic halides include dimethyl aluminum chloride, diethylaluminum chloride, dimethyl aluminum bromide, diethylaluminum bromide, dimethyl aluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethyl aluminum dichloride, and methylaluminum 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, 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, diethylaluminum iodide, di-n-butylaluminum iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methylaluminum Diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, methyl aluminum sesqui iodide, ethyl aluminum sesqui iodide, isobutyl aluminum sesqui iodide, ethyl magnesium Odide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide. odide, di-n-butyltin diiodide, or di-t-butyltin diiodide.

In addition, the catalyst composition according to an embodiment of the present invention contains the halide in an amount of 1 mole to 20 mole, more specifically 1 mole to 5 mole, more specifically 2 mole to 3 mole, per 1 mole of the neodymium compound. It can be included. If the halide is contained in a molar ratio exceeding 20, it is not easy to remove the catalytic reaction, and there is a risk that the excess halide may cause a side reaction.

Additionally, 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 tetraaryl borate anion or tetraaryl fluoride. It may be a borate anion, etc. In addition, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation along 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 (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenyl carbonium tetra It may be kiss[3,5-bis(trifluoromethyl)phenyl]borate, or N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

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

(c) Conjugated diene monomer

In addition, the catalyst composition may further include a conjugated diene-based monomer, and pre-polymerization or pre-polymerization is performed by mixing a portion of the conjugated diene-based monomer used in the polymerization reaction with the catalyst composition for polymerization in advance. By using it in the form of a premix catalyst composition, not only can the activity of the catalyst composition be improved, but also the produced active polymer can be stabilized.

In the present invention, the "preforming" refers to a catalyst composition containing a neodymium compound, an alkylating agent, and a halide, that is, when the catalyst system includes diisobutylaluminum hydride (DIBAH), etc., along with various other processes. To reduce the possibility of generating active species in the catalyst composition, a small amount of conjugated diene monomer such as 1,3-butadiene is added, which may mean that pre-polymerization occurs within the catalyst composition system with the addition of 1,3-butadiene. there is. Additionally, “premix” may mean a state in which each compound is uniformly mixed without polymerization occurring in the catalyst composition system.

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

The catalyst composition according to an embodiment of the present invention contains at least one of the above-described neodymium compound and alkylating agent, halide and conjugated diene monomer, specifically neodymium compound, alkylating agent and halide, and optionally conjugated diene monomer in an organic solvent. It can be manufactured 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 nonpolar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms, such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; A mixed solvent 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, or xylene, and any one or a mixture of two or more of these may be used. More specifically, the non-polar solvent may be a linear, branched, or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, and more specifically, n-hexane, cyclohexane, or a mixture thereof. You can.

Additionally, the organic solvent may be appropriately selected depending on the type of components constituting the catalyst composition, especially the alkylating agent.

Specifically, in the case of alkylaluminoxane such as methylaluminoxane (MAO) or ethyl aluminoxane as an alkylating agent, since it does not easily dissolve in aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent can be appropriately used.

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

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

Meanwhile, the polymerization in Step 1 may be performed as a continuous polymerization in a polymerization reactor containing at least two reactors, or may be performed in a batch reactor.

Additionally, the polymerization may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization).

Here, constant temperature polymerization refers to a polymerization method that includes the step of polymerizing with its own reaction heat without arbitrarily applying heat after adding the catalyst composition, and the elevated temperature polymerization refers to a polymerization method in which the temperature is increased by arbitrarily applying heat after adding the catalyst composition. This indicates that the isothermal polymerization refers to a polymerization method in which the temperature of the reactant is kept constant by adding heat or taking heat away after adding the catalyst composition.

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

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

In addition, the method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention includes a reaction terminator for completing the polymerization reaction, such as polyoxyethylene glycol phosphate, after preparing the active polymer; Alternatively, it may include terminating the polymerization by further using additives such as antioxidants such as 2,6-di-t-butylparacresol. In addition, additives that facilitate solution polymerization, such as chelating agents, dispersants, pH adjusters, deoxidizers, or oxygen scavengers, can optionally be used along with the reaction terminator.

Step 2 is a step of preparing a modified conjugated diene-based polymer containing a functional group by denaturing the active polymer, and can be performed by reacting the active polymer with a denaturing agent represented by Formula 1.

Typically, when an active polymer and a denaturant are reacted, as described above, the active polymer has an organometallic moiety at the terminal, so a reaction occurs between the polymer terminal and the denaturant, and a modified polymer has a structure in which a functional group derived from the denaturant is bonded to the terminal of the polymer. can only be manufactured.

However, the production method according to an embodiment of the present invention uses a denaturant represented by Chemical Formula 1, so that the reaction between the double bond in the polymer chain composed of units derived from conjugated diene monomers and the azo group in the denaturant occurs as shown in Scheme 1 below. This occurs, and as a result, a modified conjugated diene-based polymer having a structure in which the functional group derived from the denaturant is present as a linking group connecting polymer chains and the functional group derived from the denaturant is bonded to the side chain of the polymer chain can be manufactured.

[Scheme 1]

In Scheme 1, 1 represents the polymer main chain composed of units derived from conjugated diene monomers, 2 represents the denaturant, and 3 represents the structure of the polymer to which the functional group derived from the denaturant is bonded.

The denaturant 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. Specifically, the denaturant 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.

Additionally, the modifier may be used in an amount of 0.5 to 20 moles based on 1 mole of 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.

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

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

In the production method according to an embodiment of the present invention, after step 2, a modified conjugated diene-based polymer can be obtained 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. . In addition, the reaction product obtained as a result of the above reaction may include an unmodified, active polymer along with the above-described modified conjugated diene polymer.

Furthermore, the present invention provides a rubber composition containing the conjugated diene polymer and a molded article manufactured from the rubber composition.

The rubber composition according to an embodiment of the present invention contains the modified conjugated diene polymer in an amount of 0.1% by weight or more and 100% by weight or less, specifically 10% by weight to 100% by weight, and more specifically 20% by weight to 90% by weight. It may include If the content of the modified conjugated diene polymer is less than 0.1% by weight, the effect of improving the wear resistance and crack resistance of molded products, such as tires, manufactured using the rubber composition may be minimal.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene polymer. In this case, 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 natural rubber or synthetic rubber. For example, the rubber component may include natural rubber (NR) containing cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are obtained by modifying or refining the above 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, etc., and any one or a mixture of two or more of these may be used.

Additionally, the rubber composition may include 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene 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, for example, have a nitrogen adsorption specific surface area (N ₂ SA, measured in accordance with JIS K 6217-2:2001) of 20 m2/g to 250 m2/g. Additionally, the carbon black may have a dibutylphthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. If the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² /g, the processability of the rubber composition may decrease, and if it is less than 20 m ² /g, the reinforcing performance by carbon black may be minimal. In addition, if the DBP oil absorption of the carbon black exceeds 200 cc/100g, the processability of the rubber composition may decrease, and if it is less than 80 cc/100g, the reinforcement performance by the carbon black may be minimal.

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, which has the most significant effect of improving fracture properties and wet grip. In addition, the silica has a nitrogen adsorption specific surface area per gram (N ₂ SA) of 120 m2/g to 180 m2/g, and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 m2/g to 200 m2. It can be /g. If the nitrogen adsorption specific surface area of the silica is less than 120 m2/g, there is a risk that the reinforcement performance by silica may be reduced, and if it exceeds 180 m2/g, there is a risk that the processability of the rubber composition may be reduced. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m2/g, there is a risk that the reinforcement performance by silica as a filler may be reduced, and if it exceeds 200 m2/g, there is a risk that the processability 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 reinforcing properties and low heat generation properties.

The silane coupling agent specifically includes bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, and bis(3-triethoxysilylpropyl)disulfide. (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 Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis. (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl. Tetrasulfide, etc. may be mentioned, and any one or a mixture of two or more of these may be used. More specifically, considering the effect of improving reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

Additionally, the rubber composition according to one embodiment of the present invention may be sulfur crosslinkable and may further include a vulcanizing agent accordingly.

The vulcanizing agent may specifically be 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 necessary elastic modulus and strength of the vulcanized rubber composition can be secured, and at the same time, low fuel efficiency can be obtained.

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

The vulcanization accelerator is not particularly limited, and specifically includes 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 be a paraffin-based, naphthenic, or aromatic compound. More specifically, considering tensile strength and abrasion resistance, the aromatic process oil price and hysteresis loss And 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 above amount, it can prevent a decrease in the tensile strength and low heat generation (low fuel efficiency) of vulcanized rubber.

In addition, the anti-aging agent specifically includes N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- Toxi-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, etc. 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, roll, or internal mixer according to the above mixing recipe, and has low heat generation and wear resistance through a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition is used for each member of a tire such as tire tread, undertread, side wall, carcass coating rubber, belt coating rubber, bead filler, filler, or bead coating rubber, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture of various industrial rubber products.

Molded articles manufactured using the rubber composition may include tires or tire treads.

Hereinafter, the present invention will be described in more detail through examples and experimental examples. However, the following examples and experimental examples are for illustrative purposes only and do not limit the scope of the present invention.

Manufacturing 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 for reaction. Afterwards, the solvent was removed using a rotary evaporator to obtain a white solid.

Put 11 g of the white solid in a 100 ml round bottom flask, add dichloromethane (CH ₂ Cl ₂ ) and 6.0 ml of pyridine sequentially to dissolve the solid, and react while slowly adding 10.6 g of N-bromosuccinimide dropwise in a freezing point tank. I ordered it. Afterwards, the solvent was removed using a rotary evaporator, dissolved in dichloromethane, and extracted with water to obtain 11 g of a denaturant represented by the following formula 1-1 as a yellow solid (yield 91%). The denaturant of the following formula 1-1 was confirmed by observing ^{the 1} H nuclear magnetic resonance spectroscopy spectrum.

[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).

Production 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 for reaction. Afterwards, the solvent was removed using a rotary evaporator to obtain a white solid.

Put 11.4 g of the white solid in a 100 ml round bottom flask, dissolve the solid by sequentially adding dichloromethane (CH ₂ Cl ₂ ) and 6.0 ml of pyridine, and react while slowly adding 10.6 g of N-bromosuccinimide dropwise in a freezing bath. I ordered it. Afterwards, the solvent was removed using a rotary evaporator, dissolved in dichloromethane, and extracted with water to obtain 11 g of a denaturant represented by the following formula 1-2 as a yellow solid (yield 97%). The denaturant of the following formula 1-2 was confirmed by observing the ¹ H nuclear magnetic resonance spectroscopy spectrum.

[Formula 1-2]

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

Production 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 then slowly add 98 ml of 2-ethylhexyl chloroformate. The reaction was allowed to occur by adding dropwise. Afterwards, the solvent was removed using a rotary evaporator, dimethyl ether was added to dissolve it, and then extracted and separated with an aqueous NaHCO ₃ solution to obtain a pink solution.

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

Put 15.8 g of the white solid in a 100 ml round bottom flask, sequentially add dichloromethane (CH ₂ Cl ₂ ) and 5.14 ml of pyridine to dissolve the solid, and react while slowly adding 10.3 g of N-bromosuccinimide dropwise in a freezing point tank. I ordered it. Afterwards, the solvent was removed using a rotary evaporator, dissolved in dichloromethane, and extracted with water to obtain 13 g of a red denaturant represented by the following formula 1-3 (yield 82%). The denaturant of the following formula 1-3 was confirmed by observing the ¹ H nuclear magnetic resonance spectroscopy spectrum.

[Formula 1-3]

^1H 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 20L autoclave reactor, the internal temperature of the reactor was raised to 70°C. After adding the catalyst composition, polymerization was performed for 30 minutes. At this time, the catalyst composition is prepared by adding neodymium versatate (Nd(2-ethylhexanoate) ₃ ), Solvay, to n-hexane solvent, diisobutylaluminum hydride (DIBAH), and diethyl aluminum. Chloride (DEAC) was sequentially added to the neodymium versatate:DIBAH:DEAC=1:16:2.4 in a molar ratio and then mixed. After adding 6.5 mmol of the denaturant of Chemical Formula 1-1 prepared in Preparation Example 1, the denaturation reaction was performed at 70°C for 30 minutes (denaturant: 1,3-butadiene = 3.5:100 parts by weight). Afterwards, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution containing 30% by weight of antioxidant WINGSTAY (Eliokem SAS, France) dissolved in hexane, and the resulting heavy product was heated with steam. It was placed in hot water and stirred to remove the solvent, and then roll dried to remove the remaining 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 denaturant of Formula 1-2 was used instead of the denaturant 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 denaturant of Formula 1-3 was used instead of the denaturant of Formula 1-1 (modifier: 1,3-butadiene = 3.5: 100 parts by weight).

Comparative Example 1

As an unmodified butadiene polymer, CB29 (Lanxess) 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 internal temperature of the reactor was raised to 70°C. After adding the catalyst composition, polymerization was performed for 30 minutes. At this time, the catalyst composition is prepared by adding neodymium versatate (Nd(2-ethylhexanoate) ₃ ), Solvay, to n-hexane solvent, diisobutylaluminum hydride (DIBAH), and diethyl aluminum. Chloride (DEAC) was sequentially added to the neodymium versatate:DIBAH:DEAC=1:16:2.4 in a molar ratio and then mixed. Afterwards, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution containing 30% by weight of antioxidant WINGSTAY (Eliokem SAS, France) dissolved in hexane, and the resulting heavy product was heated with steam. It was placed in hot water and stirred to remove the solvent, and then roll dried to remove the remaining solvent and water to prepare an unmodified butadiene polymer.

Experimental Example 1

The physical 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 at 40°C and then loaded onto gel permeation chromatography (GPC). At this time, a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories was used. 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℃) (MU) was measured at 100℃ using a large rotor using Monsanto's MV2000E and a rotor speed of 2±0.02 rpm. The sample used at this time was left at room temperature (23 ± 3°C) for more than 30 minutes, then 27 ± 3 g was collected, filled inside the die cavity, and the Mooney viscosity was measured while operating the platen and applying torque.

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 weight average molecular weight and number average molecular weight of the polymers of Examples 1 to 3 increased compared to the polymer of Comparative Example 2, except that the polymer of Comparative Example 2 was not subjected to a denaturation reaction. It was prepared through the same method as Examples 1 to 3. This increase in molecular weight is a result indicating that in the polymers of Examples 1 to 3, the polymer chain is crosslinked by a functional group derived from the denaturant and at the same time, a functional group derived from the denaturant is introduced.

Experimental Example 2

After preparing rubber compositions and rubber specimens using the polymers of Examples 1 to 3 and Comparative Examples 1 and 2, Mooney viscosity, tensile stress, 300% modulus, wear resistance, and viscoelastic properties were measured in the following manner. Measured. The results are shown in Table 2 below.

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

(1) Preparation of rubber compositions and rubber specimens

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

For 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 the parts. Afterwards, 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, mixed gently at 50 rpm for 1.5 minutes at 50°C, and then mixed using a roll at 50°C. Thus, a vulcanized mixture in the form of a sheet was obtained. Rubber specimens were prepared by vulcanizing the obtained vulcanization mixture at 160°C for 25 minutes.

2) Comparative Example 3

For 100 parts by weight of the 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 were mixed to prepare each rubber composition. Thereafter, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), 0.5 parts by weight of vulcanization accelerator (DPG), and 3.5 parts by weight of the modifier of Formula 1-1 were added to each rubber composition and stirred at 50 rpm for 1.5 minutes at 50°C. After mild mixing, a vulcanized mixture in the form of a sheet was obtained using a roll at 50°C. Rubber specimens were prepared by vulcanizing the obtained vulcanization mixture at 160°C for 25 minutes.

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

Mooney viscosity (ML1+4, @100°C) (MU) was measured using each vulcanization formulation prepared above. Specifically, Mooney viscosity (MV) was measured using a large rotor using Monsanto's MV2000E at 100°C and a rotor speed of 2±0.02 rpm. The sample used at this time was left at room temperature (23±3°C) for more than 30 minutes, then 27±3g was collected, filled inside the die cavity, and the Mooney viscosity (FMB) was measured while operating the platen and applying torque. did.

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

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

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

(4) Abrasion resistance (DIN abrasion test)

A DIN abrasion test was performed on each rubber specimen in accordance with ASTM D5963, and was expressed as DIN wt loss index (loss volume index: ARIA (Abrasion resistance index, Method A)).

(5) Viscoelastic properties

The Tan δ property, which is most important for low fuel efficiency characteristics, was measured using DMTS 500N from Gabo, Germany, at a frequency of 10 Hz, Prestrain of 3%, and Dynamic Strain of 3% at -60°C to 60°C. At this time, the Tanδ value at 0°C indicates low road surface resistance, and the Tanδ value at 60°C indicates rolling resistance characteristics (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 tensile strength 103 103 105 100 97 98 Abrasion 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, wear resistance, and Tanδ values at 0°C of Examples 1 to 3 and Comparative Examples 2 and 3 are calculated and indexed using Equation 1 below based on the measured values of Comparative Example 1. (index), and the Tanδ value at 60°C was calculated and indexed using 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 processability equivalent to or better than Comparative Examples 1 to 3, and are significantly superior in tensile properties, wear resistance, and viscoelastic properties.

Specifically, Examples 1 to 3 had improved processability compared to Comparative Example 2, and the tensile properties, wear resistance, and viscoelastic properties (0°C Tan δ value) were all significantly greater than 5%, and Comparative Example 2 was An unmodified butadiene polymer prepared under the same conditions as Examples 1 to 3 except that it was not subjected to a denaturation reaction with the denaturant shown in , through which the modified conjugated diene polymer according to an embodiment of the present invention is represented by Formula 1 It can be confirmed that the processability, tensile properties, wear resistance, and viscoelastic properties are improved by including the functional group derived from the denaturant.

In addition, Example 1 showed equivalent processability compared to Comparative Example 3 while significantly improving tensile properties, wear resistance, and viscoelastic properties, and Comparative Example 3 showed almost the same physical properties as Comparative Example 2, which was an unmodified butadiene polymer, except for processability. . At this time, in Comparative Example 3, the modifier material presented in the present invention was used when mixing a rubber composition. These results show that the modifier represented by Chemical Formula 1 presented in the present invention is applied as a modifier during polymer production, so that the functional group derived from the modifier in the polymer molecule is formed. Its introduction has the effect of improving processability, tensile properties, wear resistance, and viscoelastic properties, and indicates that the above effects cannot be achieved when used as an additive such as a coupling agent when mixing a rubber composition.

Claims (12)

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 a monovalent hydrocarbon group having 1 to 20 carbon atoms; or -COOR ₄ , where 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 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.
In claim 1,
In Formula 1,
R ₁ and R ₃ are independently selected from the group consisting of an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an arylalkyl group with 7 to 20 carbon atoms, and -COOR ₄ It is one,
The modified conjugated diene-based polymer wherein R ₄ is an alkyl group having 1 to 10 carbon atoms.
In claim 1,
In Formula 1,
R ₁ and R ₃ are at the same time 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 ,
R ₂ is an alkylene group having 1 to 10 carbon atoms,
The modified conjugated diene-based polymer wherein R ₄ is an alkyl group having 1 to 10 carbon atoms.
In claim 1,
A modified conjugated diene-based polymer wherein the modifier 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]
.
In claim 1,
The polymer includes at least two main chains composed of units derived from conjugated diene monomers,
A modified conjugated diene-based polymer in which the two main chains are cross-linked by the action of a denaturant represented by Chemical Formula 1.
In claim 1,
The polymer is a modified conjugated diene-based polymer containing a denaturant-derived functional group represented by Formula 1 in the side chain.
In claim 1,
The polymer is a modified conjugated diene-based polymer having a weight average molecular weight of 200,000 g/mol to 1,500,000 g/mol.
1) preparing an active polymer by polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition containing a neodymium compound; and
2) A method for producing a modified conjugated diene polymer according to claim 1, comprising the step of reacting the active polymer with a modifier represented by Formula 1:
[Formula 1]

In Formula 1,
R ₁ and R ₃ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms; or -COOR ₄ , where 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 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.
In claim 8,
The catalyst composition is used in an amount such that the neodymium compound is 0.02 mmol to 0.1 mmol based on 100 g of the conjugated diene monomer.
In claim 8,
Method for producing a modified conjugated diene polymer, wherein the neodymium compound is a compound represented by the following formula (3):
[Formula 3]

In Formula 3 above,
R _a to R _c are independently hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, R _a to R _c are not all hydrogen at the same time.
In claim 8,
A method for producing a modified conjugated diene-based polymer, wherein the modifier 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 polymer according to claim 1.