WO2021049909A1 - Modified conjugated diene-based polymer, method for producing same, and rubber composition comprising same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer which has excellent tensile strength and viscoelastic characteristics as well as excellent processability, and to a rubber composition comprising same, wherein the modified conjugated diene-based polymer contains Si atoms and N atoms and has a content of the N atoms of 150 ppm or more in terms of weight and a change in Mooney viscosity (MV_R) of 20% or less.

Description

Modified conjugated diene-based polymer, method for producing the same, and rubber composition containing the same

[Mutual citation with related application]

This application claims the interest of priority based on Korean Patent Application No. 10-2019-0113004 filed on Sep. 11, 2019 and Korean Patent Application No. 10-2020-0116392 filed on Sep. 10, 2020. All contents described in the literature of the application are included as part of this specification.

[Technical field]

The present invention relates to a modified conjugated diene polymer having excellent processability and excellent tensile strength and viscoelastic properties, a method for preparing the same, and a rubber composition including the same.

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

In order to reduce the rolling 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, resilience 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 and Goodrich heat generation is preferable.

As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, and the like are known, but these have a problem of low resistance to wet road surfaces. Accordingly, recently, conjugated diene-based polymers or copolymers 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 rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. Is that it can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, reduce the movement of the chain ends by bonding or denaturation of the chain ends, and increase the bonding strength with fillers such as silica or carbon black, so that SBR by solution polymerization is not suitable for tires. It is widely used as a rubber material.

When such a solution polymerization SBR is used as a rubber material for a tire, the glass transition temperature of the rubber can be increased by increasing the vinyl content in the SBR, so that the required properties of the tire such as rolling resistance and braking force can be adjusted, as well as the glass transition temperature. Fuel consumption can be reduced by appropriate control. The solution polymerization SBR is prepared using an anionic polymerization initiator, and a technique of introducing a functional group at the terminal by bonding or denaturing the chain ends of the formed polymer using various modifiers is used. For example, U.S. Patent No. 4,397,994 proposes a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is bound using a binder such as a tin compound. I did.

On the other hand, as a modifier for introducing a functional group at the end of the polymer chain, a technique of applying an aminoalkoxysilane group modifier including an alkoxysilane group and an amine group in the molecule at the same time in order to maximize the powdery properties and reactivity of the filler is widely known. However, as the number of amine groups in the modifier increases, the solubility in the hydrocarbon solvent used for polymer production decreases, and thus it is difficult to easily perform the modification reaction.

[Prior technical literature]

(Patent Document 1) US4397994 A

The present invention has been devised to solve the problems of the prior art, and provides a modified conjugated diene-based polymer having excellent affinity with a filler by simultaneously satisfying the following conditions a) and b) and including Si atoms and N atoms. It aims to do.

In addition, the present invention provides a method for producing a modified conjugated diene-based polymer that simultaneously satisfies the conditions a) and b), comprising reacting a macromonomer including a repeating unit derived from an N-functional group-containing monomer after the modification reaction. It aims to do.

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

According to an embodiment of the present invention for solving the above problems, the present invention provides a modified conjugated diene-based polymer comprising a Si atom and an N atom and satisfying the following conditions a) and b).

a) the content of N atoms in the polymer according to NSX analysis is 150 ppm or more by weight; And

b) The Mooney viscosity change rate (MV _R ) according to the following Equation 1 is 20% or less:

[Equation 1]

MV _R = [(MV _f -MV _i ) / MV _i ] x 100

In Equation 1, MV _R is the Mooney viscosity change rate, MV _f is the 100°C Mooney viscosity after leaving the polymer at 25°C for 30 days, and MV _i is the initial 100°C Mooney viscosity of the polymer.

In addition, the present invention comprises the steps of preparing an active first chain by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator (S1); Preparing a modified active first chain by reacting the active first chain with an alkoxysilane-based compound (S2); And reacting the modified active first chain with a second chain including a repeating unit derived from an N-functional group-containing monomer (S3).

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

The modified conjugated diene-based polymer according to the present invention contains Si atoms and N atoms in the molecule, the content of the N atoms is 150 ppm or more based on the total weight of the polymer, and the Mooney viscosity change rate according to Equation 1 is 20% or less. By satisfying the conditions at the same time, it is possible to have excellent filler affinity and excellent mechanical properties.

In addition, the method for preparing a modified conjugated diene-based polymer according to the present invention comprises the step of reacting a macromonomer containing an N-functional group-containing monomer with a modified active first chain after the modification reaction, thereby A modified conjugated diene-based polymer having a viscosity change rate can be prepared.

together. The rubber composition according to the present invention includes the modified conjugated diene-based polymer, and thus has excellent tensile properties and viscoelastic properties as well as excellent processability.

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

Terms and words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

Terms

In the present specification, the term'macromonomer' refers to a unit in which two or more units derived from a polymerization-reactive monomer are repeated, and may be bonded to another polymer chain or a reactive compound through an end group.

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

In the present specification, the term'first chain' may refer to a molecular chain of a main skeleton constituting a polymer, and may refer to a chain mainly including a conjugated diene-based monomer or a repeating unit of a conjugated diene-based monomer and an aromatic vinyl-based monomer. In addition, the'second chain' may refer to a chain having a smaller number of repeating units than the first chain, and mainly including a repeating unit of an N-functional group-containing monomer.

In the present specification, the term'vinyl content' refers to the mass (or weight) of butadiene contained at positions 1 and 2 in the polymer chain based on the conjugated diene monomer (butadiene, etc.) part (total amount of polymerized butadiene) in the polymer. ) Refers to the percent.

In the present specification, the term'monovalent hydrocarbon group' means a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group. In addition, the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined according to the type of each substituent.

In the present specification, the term'divalent hydrocarbon group' refers to 2 in which carbon and hydrogen are bonded, such as a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group containing one or more unsaturated bonds, and an arylene group. It may mean a valence group of atoms, and the minimum number of carbon atoms of a substituent represented by a divalent hydrocarbon may be determined according to the type of each substituent.

In the present specification, the term'alkyl group' may mean a monovalent saturated aliphatic hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl, and butyl, and isopropyl, sec-butyl, and tertiary It may mean including all branched alkyl groups such as tert-butyl and neo-pentyl.

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

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

In the present specification, the term'alkylene group' may mean a divalent saturated aliphatic hydrocarbon such as methylene, ethylene, propylene, and butylene.

In the present specification, the term'aryl group' may mean an aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. It may mean including all of.

In the present specification, the term'heterocyclic group' refers to a cycloalkyl group or an aryl group in which a carbon atom is substituted with one or more heteroatoms, and may mean including all of a heterocycloalkyl group or a heteroaryl group.

In the present specification, the term'substitution' may mean that a functional group, an atomic group, or hydrogen of a compound is substituted with a specific substituent. When a functional group, an atomic group, or hydrogen of a compound is substituted with a specific substituent, the functional group, atomic group, or compound Depending on the number of hydrogens present, one or two or more of a plurality of substituents may be present, and when a plurality of substituents are present, each of the substituents may be the same or different from each other.

In the present specification, the term'single bond' may refer to a single covalent bond that does not include a separate atom or molecular group.

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

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

Measurement method and conditions

In the present specification, the'vinyl content' was measured and analyzed using Varian VNMRS 500 MHz NMR, and 1,1,2,2-tetrachloroethane was used as the solvent in the NMR measurement. , Solvent peak is calculated as 6.0 ppm, 7.2 to 6.9 ppm is random styrene, 6.9 to 6.2 ppm is block styrene, 5.8 to 5.1 ppm is 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm is 1, It was measured by calculating the 1,2-vinyl bond content in the entire polymer using the peak of 2-vinyl.

In the present specification,'weight average molecular weight (Mw)','number average molecular weight (Mn)' and'molecular weight distribution (MWD)' are measured through GPC (Gel permeation chromatohraph) analysis, and measured by checking the molecular weight distribution curve. will be. The molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from the measured molecular weights. Specifically, the GPC is used by combining two columns of PLgel Olexis (Polymer Laboratories) and one column of PLgel mixed-C (Polymer Laboratories), and when calculating the molecular weight, the GPC standard material is PS (polystyrene). It is carried out using, and the GPC measurement solvent is prepared by mixing 2 wt% of an amine compound in tetrahydrofuran.

In the present specification, the'N atomic content' may be measured through an NSX analysis method as an example, and the NSX analysis method is measured using a trace nitrogen quantitative analyzer (NSX-2100H). For example, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar 250 ml/min, O ₂ 350 ml/min, ozonizer 300 ml/ Set the carrier gas flow rate in min, set the heater to 800℃, and wait for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to prepare calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and obtain the area corresponding to each concentration. After that, create a straight line using the ratio of the density to the area. Thereafter, a ceramic boat containing 20 mg of a sample is placed in the auto sampler of the analyzer to obtain an area, and the N content is calculated using the area of the obtained sample and the calibration curve. At this time, the sample is a modified conjugated diene-based polymer from which the solvent is removed by placing it in hot water heated by steam and stirring. The residual monomer, residual denaturant, and oil have been removed.

In the present specification, the'Si atomic content' was measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) as an ICP analysis method. Specifically, about 0.7 g of a sample was put into a platinum crucible (Pt crucible), about 1 mL of concentrated sulfuric acid (98% by weight, Electronic grade) was added, heated at 300° C. for 3 hours, and the sample was heated in an electric furnace (Thermo Scientific, Lindberg Blue M), after conducting conversation with the program of steps 1 to 3 below,

1) step 1: initial temp 0℃, rate (temp/hr) 180 ℃/hr, temp(holdtime) 180℃ (1hr)

2) step 2: initial temp 180℃, rate (temp/hr) 85 ℃/hr, temp(holdtime) 370℃ (2hr)

3) step 3: initial temp 370℃, rate (temp/hr) 47 ℃/hr, temp(holdtime) 510℃ (3hr)

Add 1 mL of concentrated nitric acid (48 wt%) and 20 µl of concentrated hydrofluoric acid (50 wt%) to the residue, seal the platinum crucible, shake it for 30 minutes or more, and add 1 mL of boric acid to the sample. Then, the mixture was stored at 0° C. for 2 hours or more, and then diluted in 30 mL of ultrapure water, followed by inhalation and measured.

Modified conjugated diene polymer

The present invention provides a modified conjugated diene-based polymer capable of providing a rubber composition having excellent affinity with a filler and, as a result, excellent processability, tensile properties, and viscoelastic properties.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a Si atom and an N atom, and satisfies the following conditions a) and b).

a) the content of N atoms in the polymer according to NSX analysis is 150 ppm or more by weight; And

b) The Mooney viscosity change rate (MV _R ) according to the following Equation 1 is 20% or less:

[Equation 1]

MV _R = [(MV _f -MV _i ) / MV _i ] x 100

In Equation 1, MV _R is the Mooney viscosity change rate, MV _f is the 100°C Mooney viscosity after leaving the polymer at 25°C for 30 days, and MV _i is the initial 100°C Mooney viscosity of the polymer.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention includes a first chain including a repeating unit derived from a conjugated diene-based monomer; A second chain comprising a repeating unit derived from an N-functional group-containing monomer; And a unit derived from an alkoxysilane compound.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes reacting a macromonomer containing a repeating unit derived from an N-functional group-containing monomer with a modified active first chain after a modification reaction. A second chain having a rich N-functional group in the unit derived from the alkoxysilane-based compound bonded to at least one end of the polymer first chain and the first chain including a repeating unit derived from a conjugated diene-based monomer through this It may have a structure similar to the kind of graft copolymer to which this is bonded.

In this way, when all of the functional groups are intensively distributed at one end of the modified conjugated diene-based polymer, only one end of the polymer may be bonded to silica and the other end may be free when interacting with silica. Similar to that, processability can be remarkably improved by showing an excellent effect on the dispersibility of the filler and preventing aggregation. In addition, a repeating unit derived from a monomer containing an N-functional group and a unit derived from a denaturant are included at one end to which the functional group is bonded, so that the effect of the interaction with the filler can be achieved at a level equal to or higher than that of the existing modified polymer at both ends. Tensile properties and viscoelastic properties can be excellent.

In addition, in general, the modified conjugated diene-based polymer has a residue derived from a denaturant, such as an alkoxy group (-OR, where R is a hydrocarbon group) or a hydroxyl group (-OH), and condensation reaction or The storage stability decreases due to hydrolysis reaction, etc., resulting in an increase in Mooney viscosity and an increase in molecular weight distribution. Accordingly, the excellent properties of the blended properties of the modified conjugated diene-based polymer are not maintained. There is a problem that cannot be obtained. However, the modified conjugated diene-based polymer according to an embodiment of the present invention has a structure in which a second chain derived from the macromonomer is bonded to an alkoxy group, which is a moiety derived from a modifier present in the polymer, by being prepared by the method described below. And, as a result, there is no moiety derived from the denaturant in the polymer, or it is reduced compared to the existing manufacturing method.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention has the advantage of being able to introduce more functional groups than when only a modifier having a large number of functional groups is used by being prepared by a manufacturing method described below. Specifically, the alkoxy group of the active polymer and the modifier is difficult to bind two or more polymer chains to one molecule of the modifier due to steric hindrance of the polymer, and although three or more chains may be bonded, a modified polymer in which three or more chains are coupled. Is bound to be a trace amount. However, in the production method according to the present invention, the second chain derived from the macromonomer can bind the functional group to the alkoxy moiety of the modifier to which the polymer chain is bonded, regardless of the steric hindrance as described above, so that the functional group in the polymer chain is further You can introduce a lot.

That is, the introduction of a functional group in one molecule of the modifier is clearly limited, and no matter how many are introduced, the absolute functional group in the polymer is compared with the case of bonding a chain containing a functional group to an alkoxy moiety without the effect of steric hindrance as in the present invention. There must be a difference in quantity.

Accordingly, the modified conjugated diene-based polymer according to the present invention has excellent storage stability over time, so that the blending properties can maintain consistently excellent properties even at the beginning of manufacture or after time elapses, and tensile properties compared to the existing end-end modified polymer. And viscoelastic properties may be excellent.

Main parameters of modified conjugated diene polymer

According to an embodiment of the present invention, the modified conjugated diene-based polymer includes a Si atom in a molecule, and the content of the Si atom in the polymer according to ICP analysis is 50 ppm or more based on the total weight of the polymer, preferably 100 ppm or more, more preferably 180 ppm or more.

The content of the Si atom may be derived from a modifier, which is an alkoxysilane-based compound, and may occupy the main content, and may be derived from Si additionally included in the N-functional group-containing monomer in addition to being derived from the modifier. The content of the Si atom is a functional group present in the modified conjugated diene-based polymer, that is, it is expected to improve the affinity with the filler, and may be a major factor in addition to improving processability.

According to an embodiment of the present invention, the modified conjugated diene-based polymer may have a content of N atoms in the polymer according to NSX analysis of 150 ppm or more, preferably 160 ppm or more, and more preferably 170 ppm or more. The modified conjugated diene-based polymer may have a relatively high content of N atoms, and the N-functional group may have a relatively high content, and the N-functional group may be at least one end of the polymer main chain and the main chain. By having a structure bonded to the unit derived from the alkoxysilane-based compound to be bonded, the affinity and dispersibility with a filler, such as silica, are remarkably improved during the blending process, so that the viscoelastic properties are excellent and at the same time, the processability can be greatly improved.

In addition, due to such a high content of N atoms, the modified conjugated diene-based polymer according to an embodiment of the present invention may further satisfy the condition that d) the molar ratio (N/Si) of N atoms and Si atoms is 0.75 or more. have. In general, in the case of a polymer modified by a modifier, it may contain Si atoms and N atoms due to a modified polymerization initiator, a modified monomer, etc., but as described above, in the case of a polymer according to an embodiment of the present invention, an N-functional group Since the containing monomer is included as a repeating unit, the content of N atoms may be relatively large, and as a symbolic meaning, the molar ratio of N atoms and Si atoms may be 0.75 or more, preferably 0.77 or more, or 0.78 or more. , More preferably 0.8 or more, and most optimally 0.9 or more. Through this, it is possible to optimize the effect of improving processability by improving dispersibility during compounding.

According to an embodiment of the present invention, the modified conjugated diene-based polymer has a Mooney viscosity change rate (MV _R ) of 20% or less according to Equation 1 below.

[Equation 1]

MV _R = [(MV _f -MV _i ) / MV _i ] x 100

In Equation 1, MV _R is the Mooney viscosity change rate, MV _f is the 100°C Mooney viscosity after leaving the polymer at 25°C for 30 days, and MV _i is the initial 100°C Mooney viscosity of the polymer.

The Mooney viscosity change rate may be an index indicating that the increase in Mooney viscosity occurring during storage after production is small as well as processability.The polymer according to the present invention includes a second chain containing an N-functional group-containing monomer and Due to the structural characteristics in which the alkoxysilane-based compound and the first chain of the polymer are bonded to a specific structure, processability is improved, and even when stored for a long time, the change in Mooney viscosity is low, and storage stability may be excellent.

The Mooney viscosity change rate is the initial Mooney viscosity of the polymer and the rate of change in the Mooney viscosity after storing the polymer at room temperature for 30 days. In the present invention, a polymer having 20% or less is provided, and preferably 15% or less. Here, the Mooney viscosity is 100° C. Mooney viscosity, and can be measured by a conventional method applied in this technical field.

First chain containing repeating units derived from conjugated diene-based monomers

According to an embodiment of the present invention, the first chain serving as the main skeleton of the modified conjugated diene-based polymer has a repeating unit derived from a conjugated diene-based monomer as a main unit, and the conjugated diene-based monomer is, for example, 1,3-butadiene. , 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo Means a halogen atom) may be one or more selected from the group consisting of.

In addition, the first chain may further include an aromatic vinyl-based monomer in addition to the conjugated diene-based monomer to further include a repeating unit derived therefrom, and the aromatic vinyl-based monomer is, for example, styrene, α-methylstyrene, and 3-methylstyrene. , 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidinoethyl) Styrene (3-(2-pyrrolidino ethyl) styrene), 4-(2-pyrrolidino ethyl) styrene (4-(2-pyrrolidino ethyl) styrene) and 3-(2-pyrrolidino-1-methyl ethyl) It may be one or more selected from the group consisting of -α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene).

As another example, the main chain of the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with a repeating unit derived from the conjugated diene-based monomer. The diene-based monomer-derived repeating unit may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. . When the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer contains a diene-based monomer-derived repeating unit in excess of 0% to 1% by weight, more than 0% to 0.1% by weight, It may be included in an amount exceeding 0% by weight to 0.01% by weight, or exceeding 0% by weight to 0.001% by weight, and there is an effect of preventing gel formation within this range.

According to an embodiment of the present invention, when two or more monomers are included in the first chain constituting the skeleton of the modified conjugated diene-based polymer, it may be a random copolymer chain, and in this case, there is an excellent effect of having an excellent balance between physical properties. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.

Second chain containing repeating units derived from N-functional group-containing monomers

According to an embodiment of the present invention, a second chain other than the first chain is further included, and the main unit constituting the second chain is an N-functional group-containing monomer, and the N-functional group may be basically an amino group, and the aliphatic cyclic It may be an amino group, an aliphatic chain amino group, an aromatic amino group, and the like.

In addition, the modified conjugated diene-based polymer may be one in which a first chain including a repeating unit derived from a conjugated diene-based monomer is coupled through an alkoxysilyl group in the alkoxysilane-based compound, and the N-functional group is rich in the alkoxysilsilyl group. Two chains may have a bonded form.

Specifically, the N-functional group-containing monomer may be a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

X is N or CH,

R _8a to R _8c are each independently a hydrogen atom; An alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A C1-C20 heteroalkyl group, a C2-C20 heteroalkenyl group; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms,

R _8d is a single bond, a substituent substituted or unsubstituted C 1 to C 20 alkylene group; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _8e is an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms; Or a functional group represented by the following formula 1a,

O is an integer of 0 to 5 _{, at least one of R 8e} is a functional group represented by the following formula 1a, and when o is an integer of 2 to 5, a plurality of R _8e may be the same or different from each other,

[Formula 1a]

In Formula 1a,

R _8f is a single bond, an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _8g and R _8h are each independently an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A mono-, di- or tri-substituted alkylsilyl group substituted with a heterocyclic group having 3 to 20 carbon atoms or an alkyl group having 1 to 10 carbon atoms, or R _8g and R _8h are connected to each other to form a heterocyclic group having 2 to 10 carbon atoms together with N It is to form a ring group.

In addition, the N-functional group-containing monomer may be a compound represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

X ₁ -X ₂ is CH ₂ -CH ₂ or CH=CH,

X ₃ -X ₄ is CH ₂ -CH ₂ , CH=N or N=N.

In addition, the N-functional group-containing monomer may be a compound represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

R _11a and R _11b are each independently an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms; Or a functional group represented by the following formula 3a,

R _11c is an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms; Vinyl group; Or a functional group represented by the following formula 3a,

At least one of R _11a , R _11b and R _11c is a functional group represented by Formula 3a,

[Formula 3a]

In Formula 3a,

R _11d is a single bond or an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _11e and R _11f are each independently an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms; Or a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

In addition, the N-functional group-containing monomer may be a compound represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

R _12a is a single bond or an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _12b and R _12c are each independently an alkyl group having 1 to 20 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; An alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms; A heteroalkenyl group having 2 to 20 carbon atoms; A heteroalkynyl group having 2 to 20 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms; Or a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

Meanwhile, the second chain may further include a repeating unit derived from a conjugated diene-based monomer.

Modifier: alkoxysilane compound

In addition, the modified conjugated diene-based polymer may be in a form in which a second chain is coupled by an alkoxysilane-based compound, and the second chain may be a combination of an alkoxysilane-based compound as a hub, whereby the alkoxysilane-based compound is It may contain at least three Si functional groups. At this time, the meaning of three alkoxysilane groups means that there are three Si-O bonds and does not mean that there are three Si.

According to an embodiment of the present invention, the alkoxysilane-based compound included in the modified conjugated diene-based polymer may be an amine-containing alkoxysilane-based compound or an amine-free alkoxysilane-based compound.

In addition, among the alkoxysilane-based compounds, the amine-containing alkoxysilane-based compound may be a compound represented by Formula 5 below.

[Formula 5]

In Formula 5, R ¹ may be a single bond or an alkylene group having 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group having 1 to 10 carbon atoms, and R ⁴ may be hydrogen, an epoxy group, or a carbon number. It may be a 1 to 10 alkyl group, a C 2 to C 10 allyl group, a mono-, di- or tri-substituted alkylsilyl group substituted with a C 1 to C 10 alkyl group, or a C 2 to C 10 heterocyclic group, R ²¹ May be a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, and R ⁴² may be an alkylene group having 1 to 10 carbon atoms, and a and m are each independently 1 to 3 It may be a selected integer, n may be an integer of 0 to 2, j may be an integer selected from 1 to 30.

As a specific example, the compound represented by Chemical Formula 5 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(dimethoxy(methyl)silyl) )propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine(N,N-bis(3-(diethoxy(methyl)silyl) )propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(trimethoxysilyl)propyl)-methyl- 1-amine), N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine), tri (Tri(trimethoxysilyl)amine), tri(3-(trimethoxysilyl)propyl)amine (tri-(3-(trimethoxysilyl)propyl)amine), N,N-bis(3- (Diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilanamine (N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine), N- (3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine ( N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysilyl)propyl)propan-1-amine), 3-(trimethoxysilyl )-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl) Propan-1-amine (3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimehtoxysilyl)propyl)-1H-1,2,4- triazol-3-yl)propyl)propan-1-amine), N-allyl-N-(3-(trimethoxysilyl)pro Phil) prop-2-en-1amine (N-allyl-N-(3-(trimethoxysilyl)propyl)prop-2-en-1-amine), N,N-bis(oxiran-2-ylmethyl )-3-(trimethoxysilyl)propan 1-amine (N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine), 1,1,1-trimethyl-N- (3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine (1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine) and N, N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine).

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (6).

[Formula 6]

In Formula 6, R ⁵ , R ⁶ and R ⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ may each independently be an alkyl group having 1 to 10 carbon atoms And R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c may each independently be 1, 2 or 3, b+c≥4, and A is

or

In this case, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

As a specific example, the compound represented by Formula 6 is N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl Propan-1-amine (N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) and 3-(4 ,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine (3-(4,5-dihydro-1H-imidazol) It may be one selected from the group consisting of -1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (7).

[Formula 7]

In Formula 7, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms containing or not including an oxygen atom, and R ¹⁷ to R ²⁰ are each independently monovalent having 1 to 20 carbon atoms It may be a hydrocarbon group, and L ¹ to L ⁴ are each independently a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ And L ² and L ³ and L ⁴ may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring May contain 1 to 3 heteroatoms selected from the group consisting of N, O and S.

As a specific example, the compound represented by Formula 7 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N ,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)( 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetra Methoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N ,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis( N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine )(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3 -Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) (3, 3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxy Cydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine) (3 ,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrae Oxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N ,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3- Tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N ,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine)( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetra Propoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N ,N-dimethylmethan-1-amine), 3,3'-(1,1,3, 3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl )bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1 -Amine) (3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3 ,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3- diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl ))Bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine (N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3, 1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl) Bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine (N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3 -diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraprotooxide Cydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine (N,N'-((1,1, 3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1, 1,3,3-tetramethoxydisiloxane-1,3-diyl) Bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)) bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3 -Diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3 -diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane- 1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (N,N'-((1,1,3,3-tetrapropoxydisiloxane- 1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), 1,3-bis(3-(1H-imidazol-1-yl) Propyl) 1,1,3,3-tetramethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane), 1,3- Bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetraethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)- 1,1,3,3-tetraethoxydisiloxane), and 1,3-bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetrapropoxydisiloxane (1,3- It may be one selected from the group consisting of bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane).

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (8).

[Formula 8]

In Formula 8, R _b2 to R _b4 are each independently an alkylene group having 1 to 10 carbon atoms, R _b5 to R _b8 are each independently an alkyl group having 1 to 10 carbon atoms, and R _b13 and R _b14 are independently of each other It is an alkylene group of 1 to 10, R _b15 to R _b18 are each independently an alkyl group having 1 to 10 carbon atoms, and m _1, m ₂ , m ₃ and m ₄ are each independently an integer of 1 to 3.

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (9).

[Formula 9]

In Formula 9, R _e1 and R _e2 are each independently an alkylene group having 1 to 10 carbon atoms, and R _e3 to R _e6 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or -R _e7 SiR _e8 R _e9 R _e10 However, at least one of _{R e3} to R _{e6 is -R e7} SiR _e8 R _e9 R _e10 , wherein R _e7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R _e8 to R _e10 are independently of each other 1 An alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of _{R e8} to R _{e10 is an alkoxy group having 1 to 10 carbon atoms.}

As another example, the amine-free alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by Formula 10 below.

[Formula 10]

In Formula 10, X is O or S, and R _f1 and R _f2 are each independently a single bond, or an alkylene group having 1 to 10 carbon atoms,

R _f3 to R _f8 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms. , p is an integer of 0 or 1, and when p is 0, R _f1 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

As another example, the amine-free alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (11).

[Formula 11]

In Formula 11, R _g1 to R _g4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R _g5 SiOR _g6 , but R _g1 to R At least one of _{g4 is -R g5} SiOR _g6 , wherein R _g5 is a single bond or an alkylene group _{having 1 to 10 carbon atoms, R g6} is an alkyl group having 1 to 10 carbon atoms, Y is C or N, and Y is In the case of N, R _g4 does not exist.

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by Formula 12 below.

[Formula 12]

In Formula 12, R _h1 and R _h2 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R _h3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and A ₃ is -Si (R _h4 R _h5 R _h6 ) or -N[Si(R _h7 R _h8 R _h9 )] ₂ , wherein R _h4 to R _h9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms to be.

As another example, the amine-free alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (13).

[Formula 13]

In Formula 13, R _g1 to R _g3 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group _{having 1 to 10 carbon atoms, R g4} is an alkoxy group having 1 to 10 carbon atoms, and q is an integer of 2 to 100 .

Normal

The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 100,000 g/mol to 800,000 g /mol, a weight average molecular weight (Mw) of 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol, and a peak average molecular weight (Mp) may be 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol. Within this range, there are excellent effects of rolling resistance and resistance to wet road surfaces. In another example, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more and 3.0 or less, or 1.1 or more and 2.5 or less, or 1.1 or more and 2.0 or less, and tensile properties within this range And viscoelastic properties are excellent, and there is an effect of excellent balance between physical properties.

In addition, the modified conjugated diene-based polymer may have a Mooney viscosity at 100° C., 30 or more, 40 to 150, or 40 to 140, and has excellent processability and productivity within this range.

Here, the Mooney viscosity may be measured using a Mooney viscometer. Specifically, using a large rotor of Monsanto's MV2000E, under the conditions of 100°C and a rotor speed of 2±0.02 rpm, leave the polymer at room temperature (23±3°C) for 30 minutes or more, and then collect 27±3 g inside the die cavity. It was measured while filling in and applying torque by operating a platen.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, the vinyl content refers to the content of 1,2-added conjugated diene-based monomer, not 1,4-added, based on 100% by weight of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl-based monomer. I can.

Method for producing modified conjugated diene-based polymer

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

The method for preparing the modified conjugated diene-based polymer according to an embodiment of the present invention comprises polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator to prepare an active first chain. Step (S1); Preparing a modified active first chain by reacting the active main chain with an alkoxysilane-based compound (S2); And reacting a macromonomer including a repeating unit derived from the modified active first chain and an N-functional group-containing monomer (S3).

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 polymerization initiator is not particularly limited, for example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyl Lithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium , Naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide It can be more than that.

According to an embodiment of the present invention, the polymerization initiator is 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on a total of 100 g of monomers. Can be used. Here, the total of 100 g of the monomers may represent the total amount of a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer.

Step S1

The polymerization in step (S1) may be an anionic polymerization as an example, and a specific example may be a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. In addition, the polymerization in step (S1) may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (insulation polymerization), and the constant temperature polymerization includes polymerization by self-reaction heat without optionally applying heat after the polymerization initiator is added. It may mean a polymerization method, and the elevated-temperature polymerization may mean a polymerization method in which heat is arbitrarily applied after the polymerization initiator is added to increase the temperature, and the isothermal polymerization is heated by applying heat after the polymerization initiator is added. It may mean a polymerization method in which the temperature of the polymerized product is kept constant by increasing or taking away heat.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may further include a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer. There is an effect of preventing this formation. As an example of the diene-based compound, it may be 1,2-butadiene.

The polymerization of step (S1) may be carried out in a temperature range of 80°C or less, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C, or 10°C to 70°C, for example, within this range. By narrowly controlling the molecular weight distribution of the polymer, there is an excellent effect of improving physical properties.

The active polymer chain prepared by the step (S1) may mean a polymer in which a polymer anion and an organic metal cation are bonded.

Meanwhile, the polymerization of step (S1) may be carried out including a polar additive, and the polar additive is added in a ratio of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on a total of 100 g of monomers. can do. As another example, the polar additive may be added in a ratio of 0.001g to 10g, 0.005g to 5g, and 0.005g to 4g based on a total of 1 mmol of the polymerization initiator.

The polar additives include, for example, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether. , Tertiary-butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetra It may be one or more selected from the group consisting of methylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di(2-tetra) Hydrofuryl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and when the polar additive is included, conjugated diene In the case of copolymerization of the based monomer and the aromatic vinyl based monomer, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in the reaction rate thereof.

Step S2

The step (S2) is a step for preparing a modified active first chain by reacting an active first chain with an alkoxysilane-based compound, wherein the reaction may be a denaturation or a coupling reaction, wherein the denaturing agent It can be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers. As another example, the modifier may be used in a molar ratio of 1:0.1 to 10, 1: 0.1 to 5, or 1:0.1 to 1:3, based on 1 mole of the polymerization initiator in step (S1).

Step S3

In addition, the step (S3) is a step for preparing a modified conjugated diene-based polymer by reacting a macromonomer including a repeating unit derived from a monomer containing an N-functional group with a modified active first chain.

On the other hand, the manufacturing method according to an embodiment of the present invention may further include the step of preparing a macromonomer before step (S3), and the step of preparing the macromonomer includes N in the presence of an organolithium compound in a hydrocarbon solvent. -It may be performed by polymerization of a functional group-containing monomer or an N-functional group-containing monomer and a conjugated diene-based monomer. In this case, the polymerization reaction may be a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion, and thus, the macromonomer may be a living anionic end in which one end can act as a monomer.

Here, the organolithium compound may be an alkyllithium compound, specifically methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n -Decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyl It may be lithium or 4-cyclopentylium, more specifically n-butyllithium.

As an example, the macromonomer may be prepared through Reaction Scheme 1 below, and thus may be a compound having a structure represented by Formula M1 below.

[Scheme 1]

As another example, the macromonomer may be prepared through Reaction Scheme 2 below, and thus may be a compound having a structure represented by the following Chemical Formula M2.

[Scheme 2]

As another example, the macromonomer may be prepared through Reaction Scheme 3 below, and thus may be a compound having a structure represented by Formula M3 below.

[Scheme 3]

As another example, the macromonomer may be prepared through Reaction Scheme 4 below, and thus may be a compound having a structure represented by Formula M4 below.

[Scheme 4]

In Reaction Schemes 1 to 4, R _8d , R ₈ , X, X ₁ -X ₂ , X ₃ -X ₄ , R _11a to R _11c , R _12a to R _12c , and o are as defined in Chemical Formulas 1 to 4, R-Li is an alkyllithium compound, and R is an alkyl group derived from the alkyllithium. to be.

In addition, the macromonomer contains 1 to 80, 1 to 60, or 1 to 50 repeating units derived from an N-functional group-containing monomer, which is one selected from compounds represented by Chemical Formulas 1 to 4, and illustratively the above formula _{Each of r 1} to r ₄ in M1 to Formula M4 may be 1 to 80, 1 to 60, or 1 to 50. In this case, the modified conjugated diene-based polymer including the second chain derived from the macromonomer may have the aforementioned Si and N contents, and may have excellent processability, tensile properties, and viscoelastic properties in a balanced manner.

Meanwhile, the (S3) step may be to prepare a modified conjugated diene-based polymer by reacting a functional group derived from a denaturant in the modified active polymer with a macromonomer and a living anion end of the macromonomer.

Specifically, the modified active polymer chain prepared in step (S2) contains a functional group derived from a denaturant, and the functional group derived from the denaturant contains an alkoxy group remaining without reacting with the polymer chain, and thus the living anion of the macromonomer It may be that the terminal and the alkoxy group react to prepare the modified conjugated diene-based polymer.

In addition, the macromonomer may be used in an amount of 0.1 to 4.0 moles, 0.1 to 2.0 moles, or 0.5 to 1.5 moles relative to 1 mole of the polymerization initiator.

On the other hand, conventionally, a condensation reaction in which the active polymer is modified with a modifier and a compound capable of condensation with the Si-O bond of the modifier has been applied as a way to additionally introduce a functional group into the polymer. However, when the condensation reaction is used in this way, the bond between the substance having an additional functional group and the modified active polymer is formed into -Si-O-Si-, and hydrolysis may occur during the subsequent steam stripping step, washing step, or storage. Is present, and thus there is a problem in that the bond is separated at the condensation bonding site, resulting in a problem in which a functional group is lost.

On the other hand, in the case of the modified conjugated diene-based polymer prepared by the production method according to the present invention, the living end of the macromonomer reacts with the Si-OR group of the modifier to form a Si-C bond, and this bond is hydrolyzed like a condensation bond. Since it is a bond in which a reaction does not occur, there is no fear of separation, and accordingly, storage stability is improved and there is no problem of loss of the initially introduced functional group.

Rubber composition

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

The rubber composition may contain the modified conjugated diene-based polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight, and within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and excellent balance between properties.

In addition, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, and 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. As a specific example, the other rubber component 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 polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include 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.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be a silica-based filler as an example, and a specific example may be wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica, and preferably, the effect of improving fracture properties and wet It may be wet-type silica that has the best effect of both wet grip. In addition, the rubber composition may further include a carbon black-based filler if necessary.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcement and low heat generation properties may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide. , Bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) Propyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl Silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and the like, and any one or a mixture of two or more of them may be used. Preferably, when considering the effect of improving reinforcing properties, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced as a rubber component is used, the amount of the silane coupling agent is usually It may be less than the case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight based on 100 parts by weight of silica, and the effect as a coupling agent within this range is While sufficiently exerted, there is an effect of preventing the gelation of the rubber component.

The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent. The vulcanizing agent may specifically be a 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, within this range, while securing the required elastic modulus and strength of the vulcanized rubber composition, and at the same time having low fuel economy. It has an excellent effect.

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, an antioxidant, a plasticizer, an anti-aging agent, an anti-scorch agent, and zinc. white), stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is, for example, a thiazole compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering tensile strength and abrasion resistance, when considering aromatic process oil price, hysteresis loss, and low-temperature characteristics Naphthenic or paraffinic process oil may be used. For example, 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 within this range, there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

The antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol (2,6-bis( (dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio)methyl)phenol), It 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 anti-aging agent is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensation product of diphenylamine and acetone, and the like, and 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 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.

In addition, the present invention provides a tire manufactured using the rubber composition.

The tire may include a tire or a tire tread.

Example

Hereinafter, examples will be described in detail in order to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

Manufacturing Example 1

In a 500 ml round-bottom flask, 100 ml of tetrahydrofuran and 1 g (10 wt% in n-hexane) of n-butyllithium were added, and N,N-dimethyl-1-(4-vinylphenyl)methanamine (N,N After adding -dimethyl-1-(4-vinylphenyl)methanamine) (3 molar ratio to 1 mol of [act. Li]), reacted at 10° C. for 30 minutes to obtain a solution containing macromonomer (15.6 mmol/l). It was prepared, and after the reaction through GC analysis, it was confirmed that the reaction was performed through the fact that N,N-dimethyl-1-(4-vinylphenyl)methanamine was not detected.

Manufacturing Example 2

In Preparation Example 1, in place of N,N-dimethyl-1-(4-vinylphenyl)methanamine, 2-vinylpyridine (2-vinylpyridine) ([act. Li] 1 mole to 3 mole ratio) was added and reacted. Except that, a solution containing a macromonomer (15.6 mmol/l) was prepared in the same manner as in Preparation Example 1, and it was confirmed through GC analysis that the reaction was performed through the fact that 2-vinylpyridine was not detected.

Manufacturing Example 3

In Preparation Example 1, in place of N,N-dimethyl-1-(4-vinylphenyl)methanamine, 1-(4-vinylpentyl)pyrrolidine (1-(4-vinylphenethyl)pyrrolidine) ([act. Li] ] A solution containing a macromonomer (15.6 mmol/l) was prepared in the same manner as in Preparation Example 1, except that 3 molar ratio to 1 mol) was added and reacted. After the reaction through GC analysis, 1-(4 -Vinylpentyl) pyrrolidine was confirmed through the reaction was not detected.

Manufacturing Example 4

In Preparation Example 1, in place of N,N-dimethyl-1-(4-vinylphenyl)methanamine, 1-vinylpyrrolidine (1 mole ratio of [act. Li] to 3 mole ratio) was added A solution containing a macromonomer (15.4 mmol/l) was prepared through the same method as in Preparation Example 1, except for the reaction, and the reaction was performed through GC analysis through which 1-vinylpyrrolidine was not detected. Was confirmed.

Manufacturing Example 5

In Preparation Example 1, N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine (N,N ,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine) (3 mole ratio to 1 mole of [act. Li]) was added and reacted, except that the macromonomer was prepared in the same manner as in Preparation Example 1. A solution containing (15.6 mmol/l) was prepared, and after reaction through GC analysis, N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine was not detected. I did.

Manufacturing Example 6

In Preparation Example 1, in place of N,N-dimethyl-1-(4-vinylphenyl)methanamine, N,N'-dimethyl-4-methylenehexene-1-amine (N,N'-dimethyl-4-methylenehex A solution containing a macromonomer (15.6 mmol/l) in the same manner as in Preparation Example 1, except that -5-en-1-amine) (3 molar ratio to 1 mol of [act. Li]) was added and reacted. ) Was prepared, and after the reaction through GC analysis, it was confirmed that the reaction was performed through the fact that N,N'-dimethyl-4-methylenehexen-1-amine was not detected.

Comparative Production Example

In Preparation Example 1, except for reacting by adding 1,3-butadiene (15 mole ratio to 1 mole of [act. Li]) instead of N,N-dimethyl-1-(4-vinylphenyl)methanamine A solution containing a macromonomer (15.6 mmol/l) was prepared through the same method as in Preparation Example 1, and it was confirmed through GC analysis that 1,3-butadiene was not detected after the reaction.

Example 1

In a 20 L autoclave reactor, 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and then n-butyl Lithium 3.2 g (10wt% in n-hexane) was added, and the internal temperature of the reactor was adjusted to 60°C, and an adiabatic heating reaction was performed. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene. After 10 minutes, N-methyl-3-(trimethoxysilyl)-N-(3-( Trimethoxysilyl)propyl)propan-1-amine (N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) was added and reacted for 15 minutes ([DTP ]:[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=1:1 molar ratio). Thereafter, the solution containing the macromonomer prepared in Preparation Example 1 was added and reacted for 15 minutes ([act. Li]: [macromonomer] = 1:2 molar ratio), and the reaction was stopped using ethanol, and an antioxidant 33 g of a solution in which 30% by weight of Wingstay K is dissolved in hexane was added. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a modified styrene-butadiene copolymer.

Example 2

In Example 1, in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent, N-(3-(1H-imine) Dazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N-(3-(1H-imidazol-1-yl) )propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) was used in the same manner as in Example 1 to prepare a modified styrene-butadiene copolymer. ([Modifier]:[act. Li]=1:1 molar ratio).

Example 3

In Example 1, in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent, N,N'-(cyclohexane- 1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine)(N,N'-(cyclohexane-1 ,3-diyl(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) was added ([denaturant]:[act. Li]=1:1 molar ratio) ), except that the solution containing the macromonomer prepared in Preparation Example 2 as a macromonomer was added ([act. Li]: [macromonomer] = 1:2 molar ratio). A modified styrene-butadiene copolymer was prepared.

Example 4

In Example 1, in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent, 3,3'-(1,1 ,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3 -diyl)bis(N,N-diethylpropan-1-amine) was added ([denaturant]:[act. Li]=1:1 molar ratio), and a solution containing the macromonomer prepared in Preparation Example 3 as a macromonomer A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except for adding ([act. Li]:[macromonomer] = 1:2 molar ratio).

Example 5

In Example 1, in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent, 3,3'-(piperazine- 1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine)(3,3'-(piperazine-1,4-diyl)bis(N,N -bis(3-(triethoxysilyl)propyl)propan-1-amine) was added ([denaturant]:[act. Li]=1:1 molar ratio), and containing the macromonomer prepared in Preparation Example 4 as a macromonomer A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the solution was added ([act. Li]:[macromonomer] = 1:2 molar ratio).

Example 6

In Example 1, in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent, tris(3-(trimethoxysilyl) )Propyl)amine)(tris(3-(trimethoxysilyl)propyl)amine) was added ([denaturant]:[act. Li]=1:1 molar ratio), and the macromonomer prepared in Preparation Example 5 was contained as a macromonomer. A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the solution was added ([act. Li]:[macromonomer] = 1:2 molar ratio).

Example 7

In Example 1, in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent, 3,3,7,7-tetra Methoxy-5,5-bis((trimethoxysilyl)methyl)-2,8-dioxa-3,7-disilanonane (3,3,7,7-tetramethoxy-5,5-bis(( trimethoxysilyl)methyl)-2,8-dioxa-3,7-disilanonane) was added ([denaturant]:[act. Li]=1:1 molar ratio), and the macromonomer prepared in Preparation Example 6 was contained as a macromonomer. A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the solution was added ([act. Li]:[macromonomer] = 1:2 molar ratio).

Comparative Example 1

In Example 1, a solution containing the macromonomer prepared in Preparation Example 1 instead of n-butyllithium was added in an amount such that n-butyllithium of Example 1 and the macromonomer became equimolar to proceed with an adiabatic heating reaction. Then, a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the step of adding and reacting a denaturant and a macromonomer was not performed, and the reaction was stopped after capping butadiene.

Comparative Example 2

In a 20 L autoclave reactor, 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and then n-butyllithium 3.2 g (10 wt% in n-hexane) was adjusted to the internal temperature of the reactor at 60° C. and an adiabatic heating reaction was performed. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene. After 10 minutes, N-methyl-3-(trimethoxysilyl)-N-(3-( Trimethoxysilyl)propyl)propan-1-amine (N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) was added and reacted for 15 minutes ([DTP ]:[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=1:1 molar ratio). Thereafter, the reaction was stopped using ethanol, and 33 g of a solution in which 30% by weight of the antioxidant Wingstay K was dissolved in hexane was added. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a modified styrene-butadiene copolymer.

Comparative Example 3

In Comparative Example 2, tris(3-(trimethoxysilyl) instead of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 2, except that )propyl)amine was added ([DTP]:[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li] = 1:1 molar ratio).

Comparative Example 4

In Comparative Example 2, 1,1,1-trimethyl-N in place of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent -(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silinamine (1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine) was added Except for the one, a modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 2 ([DTP]:[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=1:1 Molar ratio).

Comparative Example 5

In Comparative Example 2, 2,2-dimethoxy-1-amine instead of N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as a denaturing agent Except for the addition of (3-(trimethoxysilyl)propyl)-1,2-azasilolidine (2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azasilolidine) A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 2 ([DTP]:[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=1:1 molar ratio).

Comparative Example 6

In Example 3, a solution containing the macromonomer prepared in Preparation Example 1 instead of n-butyllithium was added in an amount such that n-butyllithium of Example 3 and the macromonomer became equimolar to proceed with an adiabatic heating reaction. And, a modified styrene-butadiene copolymer was prepared in the same manner as in Example 3, except that the reaction was stopped without performing the step of adding and reacting a macromonomer after the denaturation reaction.

Comparative Example 7

In Example 6, a solution containing the macromonomer prepared in Preparation Example 5 instead of n-butyllithium was added in an amount such that n-butyllithium of Example 6 and the macromonomer became equimolar to proceed with an adiabatic heating reaction. And, a modified styrene-butadiene copolymer was prepared in the same manner as in Example 6, except that the reaction was stopped without performing the step of adding and reacting a macromonomer after the denaturation reaction.

Comparative Example 8

In Comparative Example 6, instead of tris(3-(trimethoxysilyl)propyl)amine as a denaturing agent, N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propane A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 6 except that -1-amine was added ([modifier]:[act. Li]=1:1 molar ratio).

Comparative Example 9

In Comparative Example 2, after the denaturation reaction, a solution containing the macromonomer prepared in Comparative Preparation Example was added ([act. Li]:[macromonomer]=1:2 molar ratio), followed by further reaction for 15 minutes, followed by reaction. A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 2 except for stopping ([modifier]:[act. Li]=1:1 molar ratio).

Experimental Example 1

For each modified or unmodified conjugated diene-based polymer prepared in the above Examples and Comparative Examples, the styrene unit content, vinyl content, and weight average molecular weight (Mw, X10 ³ g/mol), number average molecular weight (Mn, X10) in the polymer, respectively. ³ g/mol), molecular weight distribution (PDI, MWD), Mooney viscosity (MV), Mooney viscosity change rate, and Si and N contents were measured, respectively. The results are shown in Table 1 below.

1) Styrene unit and vinyl content (% by weight)

The contents of styrene units (SM) and vinyl (Vinyl) in each of the polymers were measured and analyzed using Varian VNMRS 500 MHz NMR.

In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 5.97 ppm, 7.2 to 6.9 ppm was random styrene, 6.9 to 6.2 ppm was block styrene, and 5.8 to 5.1 ppm was 1,4-vinyl, 5.1 to 4.5 ppm was calculated as the peak of 1,2-vinyl, and the styrene unit and vinyl content were calculated.

2) Weight average molecular weight (Mw, X10 ³ g/mol), number average molecular weight (Mn, X10 ³ g/mol), molecular weight distribution (PDI, MWD)

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through GPC (Gel permeation Chromatography) analysis, and a molecular weight distribution curve was obtained. In addition, the molecular weight distribution (PDI, MWD, Mw/Mn) was obtained by calculating from the measured molecular weights. Specifically, the GPC is used by combining two columns of PLgel Olexis (Polymer Laboratories) and one column of PLgel mixed-C (Polymer Laboratories), and when calculating the molecular weight, the GPC standard material is PS (polystyrene). It was carried out using. The GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran.

3) Mooney viscosity and Mooney viscosity change rate

The Mooney viscosity (MV, (ML1+4, @100°C) MU) was measured using a Rotor Speed 2±0.02 rpm, Large Rotor at 100°C using MV-2000 (ALPHA Technologies). Samples were left at room temperature (23±3°C) for at least 30 minutes, and then 27±3 g was collected, filled in the die cavity, and platen was operated to measure for 4 minutes.

In addition, the Mooney viscosity change rate was measured by the method described above after the same sample was allowed to stand at room temperature for 30 days, and calculated through Equation 1 below.

[Equation 1]

MV _R = [(MV _f -MV _i ) / MV _i ] x 100

In Equation 1, MV _R is the Mooney viscosity change rate, MV _f is the 100°C Mooney viscosity after leaving the polymer at 25°C for 30 days, and MV _i is the initial 100°C Mooney viscosity of the polymer.

4) Si content

The Si content was measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) by an ICP analysis method. Specifically, about 0.7 g of a sample was put into a platinum crucible (Pt crucible), about 1 mL of concentrated sulfuric acid (98% by weight, Electronic grade) was added, heated at 300° C. for 3 hours, and the sample was heated in an electric furnace (Thermo Scientific, Lindberg Blue M), after conducting conversation with the program of steps 1 to 3 below,

1) step 1: initial temp 0℃, rate (temp/hr) 180 ℃/hr, temp(holdtime) 180℃ (1hr)

2) step 2: initial temp 180℃, rate (temp/hr) 85 ℃/hr, temp(holdtime) 370℃ (2hr)

3) step 3: initial temp 370℃, rate (temp/hr) 47 ℃/hr, temp(holdtime) 510℃ (3hr)

Add 1 mL of concentrated nitric acid (48 wt%) and 20 µl of concentrated hydrofluoric acid (50 wt%) to the residue, seal the platinum crucible, shake it for 30 minutes or more, and add 1 mL of boric acid to the sample. Then, the mixture was stored at 0° C. for 2 hours or more, and then diluted in 30 mL of ultrapure water, followed by inhalation and measured.

5) N content

The N content was measured using an NSX analysis method, a trace nitrogen quantitative analyzer (NSX-2100H). Specifically, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), _{set the carrier gas flow rate to 250 ml/min for Ar, 350 ml/min for O 2} , and 300 ml/min for ozonizer, and heater After setting at 800° C., the analyzer was stabilized by waiting for about 3 hours. After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to prepare calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and obtain the area corresponding to each concentration. After that, a straight line was created using the ratio of the density to the area. Thereafter, a ceramic boat containing 20 mg of a sample was placed on the auto sampler of the analyzer and measured to obtain an area. The N content was calculated using the obtained sample area and the calibration curve.

As shown in Table 1, in Examples 1 to 7, the content of N atoms is 150 ppm or more, the content of Si atoms is 50 ppm or more, and the Mooney viscosity change rate is 20% or less, and conditions suggested by the present invention a) It was confirmed that both and b) were satisfied.

On the other hand, in Comparative Examples 1 to 9, the content of N atoms was less than 150 ppm, or the Mooney viscosity change rate exceeded 20%, so that the conditions a) and b) presented in the present invention were not satisfied at the same time. At this time, Comparative Example 1 is a polymer prepared by using the macromonomer presented in the present invention as a modified polymerization initiator, and without performing the modification reaction and the reaction with the macromonomer after the polymerization reaction. It is a polymer prepared without using the macromonomer presented in the present invention, and Comparative Examples 6 to 8 were performed without performing the step of reacting with the macromonomer after the denaturation reaction using the macromonomer presented in the present invention as a modified polymerization initiator. And Comparative Example 9 is a polymer prepared using a macromonomer that does not contain a repeating unit derived from an N-functional group-containing monomer.

From the results shown in Table 1 above, the modified conjugated diene-based polymer according to an embodiment of the present invention is an active first chain modified with a macromonomer containing a repeating unit derived from an N-functional group-containing monomer after the modification reaction presented in the present invention. It can be seen that it is prepared through a manufacturing method including the step of reacting with and can have properties that simultaneously satisfy conditions a) and b).

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions including the modified styrene-butadiene copolymers prepared in Examples and Comparative Examples and molded articles prepared therefrom, tensile properties and viscoelastic properties were measured, respectively, and the results are shown in Table 3 below. Shown in.

1) Preparation of rubber specimen

Each modified or unmodified conjugated diene-based polymer of Examples, Comparative Examples and Reference Examples was used as a raw material rubber and was blended under the blending conditions shown in Table 2 below. The content of the raw materials in Table 2 is each part by weight based on 100 parts by weight of the raw rubber.

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first-stage kneading, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc agent (ZnO), stearic acid are used using a Banbari mixer attached with a temperature control device. , Antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) At this time, the initial temperature of the kneader was controlled at 70° C., and after completion of the blending, a first blend was obtained at a discharge temperature of 145° C. to 155° C. In the second stage kneading, the first blend was cooled to room temperature. After that, the first blend, sulfur, a rubber accelerator (DPG (diphenylguanidine)) and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and at a temperature of 100°C or less. The mixture was mixed to obtain a second blend, and then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

2) Tensile characteristics

For tensile properties, each test piece was prepared according to the tensile test method of ASTM 412, and the tensile stress (300% modulus) at the time of 300% elongation of the test piece was measured. Specifically, tensile properties were measured at a rate of 50 cm/min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.

3) Viscoelastic properties

For viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60℃~60℃) in Film Tension mode using a dynamic mechanical analyzer (GABO). In the measurement result, the higher the low temperature 0℃ tan δ value, the better the wet road surface resistance, and the lower the high temperature 60℃ tan δ value, the lower the hysteresis loss and the better the rolling resistance (fuel economy). Since the result value is expressed in Index (%) based on the result value of Comparative Example 1, the higher the value, the better.

4) Processability characteristics

1) The Mooney viscosity (MV, (ML1+4, @100°C) MU) of the first compound obtained during the manufacture of the rubber specimen was measured to compare and analyze the processability characteristics of each polymer. It indicates excellent processability characteristics, and in Table 3 below, it is expressed as an Index (%) based on the result value of Comparative Example 3. The higher the value, the better.

Specifically, MV-2000 (ALPHA Technologies, Inc.) was used at 100°C with a Rotor Speed of 2±0.02 rpm, and a Large Rotor was used, and each of the primary formulations was left at room temperature (23±3°C) for 30 minutes or more, and then 27 ±3 g was collected, filled inside the die cavity, and measured for 4 minutes by operating the platen.

As shown in Table 3, it was confirmed that Examples 1 to 7 exhibited excellent processability properties compared to Comparative Examples 1 to 9, and at the same time excellent tensile properties and viscoelastic properties were also excellent. While exhibiting a tensile property equal to or higher than that, it exhibited improved viscoelastic properties and remarkably improved processability properties. Here, Comparative Examples 1 to 9 are polymers that do not simultaneously satisfy the conditions a) and b) presented in the present invention.

Through the above Tables 1 and 3, the modified conjugated diene-based polymer of the present invention can satisfy conditions a) and b) at the same time by being prepared by a manufacturing method comprising the step of reacting with a macromonomer after the denaturation reaction. Comparative Examples 1 to 9, in particular Comparative Examples 6 to 8, it can be confirmed that a remarkable effect can be exhibited, and through this difference in effect, the modified conjugated diene-based polymer of the present invention has a structure different from that of Comparative Examples 6 to 8. A second chain containing a repeating unit derived from a copolymer, such as an N-functional group-containing monomer derived from a macromonomer, is coupled to the first chain of a modified polymer by a functional group derived from a denaturant to form the same structure as a graft copolymer. Can be predicted.

Claims (17)

1. A modified conjugated diene-based polymer containing Si atom and N atom and satisfying the following conditions a) and b):

   a) the content of N atoms in the polymer according to NSX analysis is 150 ppm or more by weight; And

   b) The Mooney viscosity change rate (MV _R ) according to the following Equation 1 is 20% or less:

   [Equation 1]

   MV _R = [(MV _f -MV _i ) / MV _i ] x 100

   In Equation 1, MV _R is the Mooney viscosity change rate, MV _f is the 100°C Mooney viscosity after leaving the polymer at 25°C for 30 days, and MV _i is the initial 100°C Mooney viscosity of the polymer.
2. The method according to claim 1,

   The modified conjugated diene-based polymer d) a modified conjugated diene-based polymer having a molar ratio (N/Si) of an N atom and a Si atom of 0.75 or more.
3. The method according to claim 1,

   The modified conjugated diene-based polymer is a modified conjugated diene-based polymer having an N atom content of 170 ppm or more based on weight.
4. The method according to claim 1,

   The modified conjugated diene-based polymer is a modified conjugated diene-based polymer having a Mooney viscosity change rate (MV _R ) of 15% or less according to Equation 1.
5. The method according to claim 1,

   The modified conjugated diene-based polymer in which the content of Si atoms in the polymer according to ICP analysis is 50 ppm or more based on weight.
6. The method according to claim 1,

   A first chain comprising a repeating unit derived from a conjugated diene-based monomer; A second chain comprising a repeating unit derived from an N-functional group-containing monomer; And a unit derived from an alkoxysilane-based compound.
7. The method of claim 6,

   The alkoxysilane-based compound is a modified conjugated diene-based polymer that is an amine-containing alkoxysilane-based compound or an amine-free alkoxysilane-based compound.
8. The method of claim 6,

   The first chain is a modified conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl-based monomer.
9. The method of claim 6,

   The second chain is a modified conjugated diene-based polymer further comprising a unit derived from a conjugated diene-based monomer.
10. The method according to claim 1,

    The number average molecular weight (Mn) is 1,000 g/mol to 2,000,000 g/mol, the weight average molecular weight (Mw) is 1,000 g/mol to 3,000,000 g/mol, and the peak average molecular weight (Mp) is 1,000 g/mol to 3,000,000 g /mol modified conjugated diene-based polymer.
11. Preparing an active first chain by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a polymerization initiator (S1);

    Preparing a modified active first chain by reacting the active first chain with an alkoxysilane-based compound (S2); And

    A method for producing a modified conjugated diene-based polymer of claim 1, comprising reacting (S3) a macromonomer comprising a repeating unit derived from the monomer containing the modified active first chain and an N-functional group.
12. The method of claim 11,

    The method for producing a modified conjugated diene-based polymer wherein the macromonomer further comprises a unit derived from a conjugated diene-based monomer,
13. The method of claim 11,

    The macromonomer is a method for producing a modified conjugated diene-based polymer to be prepared by a low polymerization reaction of an N-functional group-containing monomer or an N-functional group-containing monomer and a conjugated diene-based monomer in the presence of an organolithium compound in a hydrocarbon solvent.
14. The method of claim 11,

    The alkoxysilane-based compound is a method for producing a modified conjugated diene-based polymer to be used in an amount of 0.1 to 10 moles relative to 1 mole of the polymerization initiator.
15. The method of claim 11,

    The method for producing a modified conjugated diene-based polymer, wherein the macromonomer is used in an amount of 0.1 to 4.0 moles relative to 1 mole of the polymerization initiator.
16. A rubber composition comprising the modified conjugated diene polymer and a filler according to claim 1.
17. The method of claim 16,

    The rubber composition is a rubber composition containing 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.