WO2021049913A1 - Modified conjugated diene-based polymer and rubber composition comprising same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer having excellent processability as well as excellent tensile strength and viscoelasticity properties, and a rubber composition comprising same, and provides a modified conjugated diene-based polymer comprising: a unit derived from a modifier having at least three alkoxy silane groups; a non-functional chain which forms a silicon-carbon bond on one side of the modifier-derived unit and includes a conjugated diene-based monomer derived-repeat unit; and a functional chain which forms a silicon-carbon bond on the other side of the modifier-derived unit and includes at least two units of an N-functional group-containing monomer-derived unit.

Description

Modified conjugated diene polymer and rubber composition comprising the same

Mutual citation with related applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0113004 filed on September 11, 2019 and Korean Patent Application No. 10-2020-0116402 filed on September 10, 2020. All contents disclosed in the literature are included as part of this specification.

Technical field

The present invention relates to a modified conjugated diene-based polymer having excellent processability and excellent tensile strength and viscoelastic properties, and a rubber composition comprising 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 generation, 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-polymerized 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 running 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 Literature]

(Patent Document 1) US4397994 A

The present invention was conceived to solve the problems of the prior art, and through the arrangement of a non-functional chain, a denaturant-derived unit, and a functional chain rich in an N-functional group, it has excellent affinity with a filler, while simultaneously processing and abrasion resistance. It is an object to provide an excellent modified conjugated diene-based polymer.

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 is a unit derived from a denaturant having 3 or more alkoxy groups bonded to silicon; A non-functional chain including a repeating unit derived from a conjugated diene-based monomer and forming a silicon-carbon bond at one side of the unit derived from the denaturant; And it provides a modified conjugated diene-based polymer comprising a; and a functional chain that forms a silicon-carbon bond on the other side of the unit derived from the denaturant and includes at least two units derived from the monomer-containing N-functional group.

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

The modified conjugated diene polymer according to the present invention introduces a functional chain in order to abundantly distribute the functional groups interacting with the filler, and by appropriately arranging the functional chain, the unit derived from the denaturant, and the non-functional chain, It has excellent chemical conversion properties and may have excellent mechanical properties.

together. The rubber composition according to the present invention has the effect of improving abrasion resistance while having excellent processability as well as tensile properties and viscoelastic properties by including the modified conjugated diene-based polymer.

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.

Definition of Terms

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'functionality' may mean that it contains a functional group and thus has a characteristic capable of reacting with other functional groups or active sites, and in addition to a bond between carbons or between carbons and hydrogens, N, O, S or It may mean a characteristic having a functional group including Si.

In the present specification, the term'non-functional 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. have.

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 an 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 unit derived from a modifier having 3 or more alkoxy groups bonded to silicon; A non-functional chain including a repeating unit derived from a conjugated diene-based monomer and forming a silicon-carbon bond at one side of the unit derived from the denaturant; And a functional chain that forms a silicon-carbon bond at the other side of the unit derived from the modifier and includes at least two units derived from the monomer-containing N-functional group.

In the modified conjugated diene-based polymer, the content of N atoms in the polymer according to NSX analysis may be 100 ppm or more, preferably 150 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 by introducing a functional chain having an N-functional group repeatedly present, and the N-functional group is bonded to the polymer main chain and at least one end of the main chain By having a structure bonded to the unit derived from the alkoxysilane-based compound, the affinity and dispersibility with a filler, such as silica, are remarkably improved in the blending process, so that the viscoelastic properties are excellent and the processability can be greatly improved. On the other hand, when the content of the N atom is applied to that the alkoxysilane modifier contains an amine, N atoms derived from the modifier may also be present.

According to an embodiment of the present invention, the modified conjugated diene-based polymer may have a content of Si atoms in the polymer according to ICP analysis of 180 ppm or more based on weight, preferably 190 ppm or more, more preferably 200 ppm or more. I can.

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.

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 satisfy the condition that the molar ratio (N/Si) of N atoms and Si atoms is 0.75 or more. 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.

Modified conjugated diene polymer structure

According to an embodiment of the present invention, the modified conjugated diene-based polymer includes a non-functional chain and a functional chain, and the non-functional chain and the functional chain have a structure in which they are mutually bonded through a unit derived from a denaturant. A non-functional chain and a functional chain are bonded (or coupled) around the unit derived from the denaturant, and the non-functional chain and the functional chain may each independently be bonded to one or more chains, preferably functional The chain may be a combination of two or more chains.

The functional chain and the non-functional chain are bonded to each other with the unit derived from the modifier interposed therebetween may be due to a reaction between the living anion end of each chain and the Si-bonded alkoxy group of the modifier. That is, the above structure can be implemented through a denaturation reaction and a pseudomodification reaction after polymerization.

In the case of the structure as described above, all functional groups are distributed at one end of the polymer, and when interacting with silica, only one end of the polymer may be bonded to silica and the other end may be free. Accordingly, it is similar to the existing end-modified polymer. Excellent processability can be achieved by showing an excellent effect on the dispersibility of the filler and preventing agglomeration.

In addition, in the existing both-end modified polymer, it is common for functional group-containing monomers to be bonded to the other end different from the unit derived from the denaturant, and when this structure is adopted, the viscoelastic properties can be improved by improving the affinity with the filler due to the rich functional groups. However, there is a problem in that the degree of freedom of the polymer structure is significantly reduced, and the processability is very poor. However, in the case of the modified conjugated diene-based polymer according to the present invention, by having a structure in which the functional chain is adjacent to the unit derived from the denaturant, the effect of improving the viscoelastic properties by interaction with the filler at an equivalent level or higher can be achieved. , Improvement in workability can be remarkably achieved.

In addition, since the functional chain is present at the same end as the unit derived from the denaturant, synergy is generated in the interaction with the filler, so that a great effect can be seen in improving the abrasion resistance.

That is, according to an embodiment of the present invention, a functional chain including a repeating unit derived from a monomer-containing N-functional group and a unit derived from a denaturant are intensively disposed on one side of the entire polymer, so that the conventional terminal modified conjugated diene system Polymers, modified conjugated diene-based polymers at both ends, and modified conjugated diene-based polymers in the human body have advantages, but problems can be solved.

Non-functional chain containing repeating units derived from conjugated diene-based monomers

According to an embodiment of the present invention, the non-functional 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 non-functional 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)styrene).

As another example, the non-functional 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 the 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 non-functional 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.

The non-functional chain of the modified conjugated diene-based polymer according to an embodiment of the present invention may not contain a functional group, wherein the functional group is an N-containing functional group, an S-containing functional group, an O-containing functional group, or a Si-containing functional group. Can be As described above, by not distributing a functional group in one non-functional chain, the effect of arranging the functional chain at one end so as to be adjacent to the unit derived from the denaturant can be achieved.

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

According to an embodiment of the present invention, the functional chain of the modified conjugated diene-based polymer includes a repeating unit derived from an N-functional group-containing monomer.

According to an embodiment of the present invention, the main unit constituting the functional chain is an N-functional group-containing monomer, and the N-functional group may be essentially an amino group, an aliphatic cyclic amino group, an aliphatic chain amino group, an aromatic amino group, etc. have.

In addition, one unit of the functional chain may be coupled to a unit derived from a modifier, and the functional chain may be coupled through two or more alkoxysilyl groups in which two or more units are present in the alkoxysilane modifier.

The functional chain is a form in which an N-functional group-containing monomer is repeatedly bonded, and the number of repeating units may be 2 to 80. When the number of repeating units is 2 to 80, it is possible to secure a desired level of functional groups by arranging the functional chain on the structure, so that both processability and blending properties can be achieved.

The functional chain may further include a unit derived from a conjugated diene-based monomer. That is, in the case of a functional chain, it can be polymerized (low polymerization) only with an N-functional group-containing monomer, but for the purpose of increasing the molecular weight or length, the N-functional group-containing monomer and the conjugated diene-based monomer can be polymerized together (low polymerization). May be. In this case, the functional chain may be in the form of a random copolymer in which the conjugated diene-based monomer and the N-functional group-containing monomer are arbitrarily arranged, or in the form of a block copolymer in which the same units are gathered and arranged, and there is no limitation on this form.

The weight average molecular weight of the functional chain may be less than the weight average molecular weight of the non-functional chain, for example, may be 50% or less, 30% or less of the weight average molecular weight of the non-functional chain, and preferably 10 % Or less, more preferably 5% or less. This is a level at which the non-functional chain can be bonded to the alkoxy moiety present in the modifier to which the non-functional chain is bound, and a difference sufficient to overcome the steric hindrance of the non-functional chain modified or coupled with a modifier is sufficient. It's not a criterion for having to be a degree.

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 means to additionally introduce a functional group into the polymer. However, when the condensation reaction is used in this way, the bond between the material having an additional functional group and the modified polymer is formed into -Si-O-Si-, and there is a possibility that hydrolysis may occur during the subsequent steam stripping step, washing step, or storage. Exist, and thus there is a problem in that the bond is separated at the condensation bonding site, and eventually a problem occurs in that a functional group is lost.

On the other hand, in the case of the modified conjugated diene-based polymer according to the present invention, the living end of the functional chain reacts with the Si-OR group of the modifier to form a Si-C bond, and this bond does not undergo a hydrolysis reaction like a condensation bond. Since it is a bond, 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.

According to an exemplary embodiment of the present invention, the N-functional group-containing monomer may be, for example, 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 4a,

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 4a,

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.

Modifier: alkoxysilane compound

In addition, the modified conjugated diene-based polymer may be in a form in which a non-functional chain and a functional chain are coupled by an alkoxysilane-based modifier, and the non-functional chain and the functional chain may be bonded to the alkoxysilane-based modifier as a hub. Therefore, the alkoxysilane modifier may be one containing at least three alkoxy groups bonded to Si.

According to an embodiment of the present invention, the alkoxysilane-based modifier 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 modifiers, the amine-containing alkoxysilane 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 modifiers may include a compound represented by the following formula (6).

[Formula 6]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.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 modifiers 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, Rf1 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 wet road surface resistance. 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±5°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 non-functional chain. Step (S1); Preparing a modified active non-functional chain by reacting the active non-functional chain with an alkoxysilane-based modifier (S2); And reacting the modified active non-functional chain with a functional chain including a repeating unit derived from 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 non-functional chain by reacting an active non-functional chain with an alkoxysilane-based compound, wherein the reaction may be a modification or a coupling reaction, in which case, the modifying 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 modified active non-functional chain with a functional chain including a repeating unit derived from an N-functional group-containing monomer.

On the other hand, the manufacturing method according to an embodiment of the present invention may further include the step of preparing a functional chain before step (S3), and the step of preparing the functional chain includes the presence of an organolithium compound in a hydrocarbon solvent. It may be carried out by polymerization reaction of an N-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 functional chain 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 functional chain may be prepared through Reaction Scheme 1 below, and thus may be a compound having a structure represented by the following Chemical Formula M1.

[Scheme 1]

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

[Scheme 3]

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

[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 functional chain 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 In Formulas M1 to M4, _{each of r 1} to r ₄ 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 functional chain may have the aforementioned Si and N contents, and may have excellent processability, tensile properties, and viscoelastic properties in a balanced manner.

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

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

In addition, the functional chain 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.

When applying the manufacturing method according to an embodiment of the present invention, there is an advantage in that more functional groups can be introduced than when only a modifier having a large number of functional groups is used. 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, as in the present invention, the functional chain having a weight average molecular weight of about 10% level than that of the non-functional chain can overcome the steric hindrance effect, and accordingly, the denaturant in which one or two non-functional chains are bound The ability to bind to the alkoxy moiety allows the introduction of more functional groups in the polymer chain.

In other words, the introduction of a functional group in one molecule of the denaturant is clearly limited, and even if it is introduced, it is an absolute amount compared to the case where a functional chain of a level that does not receive steric hindrance effect as in the present invention is bonded to an alkoxy moiety. There must be a difference.

Accordingly, the modified conjugated diene-based polymer prepared by the method for producing a modified conjugated diene-based polymer according to the present invention may have excellent tensile properties and viscoelastic properties compared to the existing terminal-end modified polymer. In addition, since it is a method using an alkoxy moiety, non-functional properties can be maintained at the start end for additional introduction of a functional group, so processing characteristics can be significantly improved compared to the existing modified polymer at both ends, and the alkoxy remaining in the unit derived from the denaturant Since the residue can be reduced compared to the existing manufacturing method, side reactions such as condensation reactions or hydrolysis reactions occurring due to the presence of -OR groups or -OH groups in the polymer can be significantly reduced, improving processability and significantly changing over time. As it is reduced, storage stability can also be improved.

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.

Experiment #1

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 1-vinyl-1H-imidazole was added ( [act. Li] 3 mol ratio to 1 mol), and reacted at 10° C. for 30 minutes to prepare a solution containing a functional chain (15.6 mmol/l), and 1-vinyl-1H after the reaction through GC analysis -It was confirmed that the reaction was carried out through the fact that imidazole was not detected.

Example 1-1

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, and after 10 minutes elapsed, 1,1,1-trimethyl-N-(3-(triethoxysilyl) as a denaturant Profile)-N-(trimethylsilyl)silanamine (1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine) was added and reacted for 15 minutes ([DTP] :[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=0.7:1 molar ratio). Thereafter, the solution containing the functional chain prepared in Preparation Example 1 was added and reacted for 15 minutes ([act. Li]:[functional chain]=1:1 molar ratio), and the reaction was stopped using ethanol, 33 g of a solution in which the antioxidant Wingstay K was dissolved in 30% by weight 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 1-2

In Example 1-1, in place of 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silaneamine as a denaturing agent, 3-(2,2-dime Toxic-1,2-azaciloridin-1-yl)-N,N-bis(3-(trimethoxysilyl)propyl)propan-1-amine (3-(2,2-dimethoxy-1,2 -Azasilodidin-1-yl) -N,N-bis (3- (trimethoxysilyl) propyl) propan-1-amine), except for using the same procedure as in Example 1-1, modified styrene-butadiene copolymer Was prepared ([modifier]:[act. Li]=0.7:1 molar ratio).

Comparative Example 1-1

In Example 1-1, a solution containing the functional chain prepared in Preparation Example 1 instead of n-butyllithium was added in an amount such that n-butyllithium of Example 1-1 and the functional chain were equimolar. The modified styrene-butadiene copolymer was carried out in the same manner as in Example 1-1, except that the reaction was stopped after capping butadiene without performing an adiabatic heating reaction, and then adding and reacting a denaturant and a functional chain. The coalescence was prepared.

Comparative Example 1-2

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, and after 10 minutes elapsed, 1,1,1-trimethyl-N-(3-(triethoxysilyl) as a denaturant Profile)-N-(trimethylsilyl)silanamine (1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine) was added and reacted for 15 minutes ([DTP] :[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=0.7:1 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 1-3

In Comparative Example 1-2, a solution containing the functional chain prepared in Preparation Example 1 instead of n-butyllithium was added in an amount such that n-butyllithium of Comparative Example 1-2 and the functional chain became equimolar. A modified styrene-butadiene copolymer was prepared in the same manner as Comparative Example 1-2, except that the adiabatic heating reaction was performed ([DTP]:[act. Li]=1.5:1 molar ratio, [modifier]: [act. Li] = 0.7:1 molar ratio).

Evaluation of polymer properties

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

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), and the sample used at this time Was left at room temperature (23±3℃) for at least 30 minutes, and then 27±3 g was collected, filled inside the die cavity, and the platen was operated to measure for 4 minutes.

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 1-1 and 1-2, Si and N atoms were present in the polymer molecule, and the content of N atoms was significantly increased compared to Comparative Example 1-1. At this time, Comparative Example 1-1 was a polymer prepared without using a modifier, and it was confirmed that the Si atom was not present, and in Comparative Example 1-2, it was confirmed that the N content was significantly small due to the absence of a functional chain. have.

Evaluation of properties of rubber molded products

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 mixing, a first compound was obtained at a discharge temperature of 145° C. to 155° C. In the second stage kneading, the first compound was cooled to room temperature. After that, the first compound, sulfur, a rubber accelerator (DPD (diphenylguanine)) 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℃ tanδ value, the better the wet road surface resistance, and the lower the high temperature 60℃ tanδ value, the lower the hysteresis loss and the better low running resistance (fuel economy). The value is expressed in Index (%) based on the result value of Comparative Example 1-1, so the higher the value, the better.

4) Processability characteristics

1) The Mooney viscosity (MV, (ML1+4, @100°C) MU) of the secondary 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 in Index (%) based on the result value of Comparative Example 1-1. 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 secondary compound 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.

* All of the above indices are values based on Comparative Example 1-1.

As shown in Table 3, in the case of Examples 1-1 and 1-2 using the modified conjugated diene-based polymer according to an embodiment of the present invention, while exhibiting excellent processability properties compared to Comparative Examples 1-1 to 1-3, at the same time It was confirmed that the tensile properties and viscoelastic properties were also excellent.

When comparing Examples 1-1 and 1-2 with Comparative Examples 1-1 and 1-2, it can be seen that a very remarkable difference is shown in rotational resistance and tensile properties are also improved, compared to Comparative Example 1-3. While exhibiting equal or higher tensile properties, improved viscoelastic properties and remarkably improved processability properties were exhibited.This is because the functional chain in the examples was used together with the modification initiator, and the functional chain was not bonded to the modifying agent. It can be seen that this is because there is a very remarkable difference.

Through this, it can be confirmed that the modified conjugated diene-based polymer of the present invention can exhibit a remarkable effect that is not expressed in Comparative Example 1-3 by being prepared by a manufacturing method comprising the step of reacting with a functional chain after the denaturation reaction. , Through this difference in effect, the modified conjugated diene-based polymer of the present invention is a copolymer having a structure different from Comparative Example 1-3, for example, a functional chain including a repeating unit derived from an N-functional group-containing monomer derived from a functional chain is modified. It can be predicted that the non-functional chain of the resulting polymer is coupled by a functional group derived from a modifier to form a structure similar to that of the graft copolymer.

Experiment #2

Manufacturing Example 2

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'-diethyl-N,N'-diisopropyl-1,1 -After adding divinylsilanediamine (N,N'-diethyl-N,N'-diisopropyl-1,1-divinylsilanediamine) (3 mole ratio to 1 mole of [act. Li]), reacted at 10°C for 30 minutes To prepare a solution containing a functional chain (15.6 mmol/l), and after reaction through GC analysis, N,N'-diethyl-N,N'-diisopropyl-1,1-divinylsilanediamine It was confirmed that the reaction was performed through what was not detected.

Example 2-1

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,N-diethyl-3-(trimethoxysilyl)propane-1- An amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine) was added and reacted for 15 minutes ([DTP]:[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=0.7:1 molar ratio). Thereafter, the solution containing the functional chain prepared in Preparation Example 2 was added and reacted for 15 minutes ([functional chain]:[act. Li] = 1:1 molar ratio), and the reaction was stopped using ethanol, and 33 g of a solution in which the antioxidant Wingstay K was dissolved in 30% by weight 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 2-2

In Example 2-1, in place of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a denaturing agent, N,N-bis(oxiran-2-ylmethyl)-3-( Same as in Example 2-1, except that trimethoxysilyl)propan-1-amine (N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine) was added. To prepare a modified styrene-butadiene copolymer ([modifier]:[act. Li]=0.7:1 molar ratio).

Comparative Example 2-1

In Example 2-1, a solution containing the functional chain prepared in Preparation Example instead of n-butyllithium was added in an amount such that n-butyllithium of Example 2-1 and the functional chain became equimolar, Modified styrene-butadiene copolymer was carried out in the same manner as in Example 2-1, except that the adiabatic heating reaction was performed, and then the reaction was stopped after capping butadiene without performing the step of adding and reacting a denaturant and a functional chain. Was prepared.

Comparative Example 2-2

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,N-diethyl-3-(trimethoxysilyl)propane-1- The amine was added and reacted for 15 minutes ([DTP]:[act. Li]=1.5:1 molar ratio, [modifier]:[act. Li]=0.7:1 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 2-3

In Comparative Example 2-2, in place of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a denaturing agent, 3,3'-(1,1,3,3-tetramethoxydisiloxane A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 2-2, except that -1,3-diyl)bis(N,N-diethylpropan-1-amine) was added ([ Denaturant]:[act. Li]=0.7:1 molar ratio).

Comparative Example 2-4

In Comparative Example 2-2, a solution containing the functional chain prepared in Preparation Example 2 instead of n-butyllithium was used in an amount such that n-butyllithium and the functional chain of Comparative Example 2-2 became equimolar. A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 2-2, except that the adiabatic heating reaction was performed by adding.

Comparative Example 2-5

In Comparative Example 2-4, in place of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a denaturing agent, 3,3'-(1,1,3,3-tetramethoxydisiloxane A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 2-4, except that -1,3-diyl)bis(N,N-diethylpropan-1-amine) was added ([ Denaturant]:[act. Li]=0.7:1 molar ratio).

Evaluation of polymer properties

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 in the same manner as in Experiment #1, respectively. The results are shown in Table 4 below.

As shown in Table 4, in Examples 2-1 and 2-2, Si and N atoms were present in the polymer molecule, and it can be seen that the content of N atoms was significantly increased compared to Comparative Examples 2-1 to 2-3. .

Evaluation of properties of rubber molded products

In order to compare and analyze the physical properties of the rubber composition containing each modified styrene-butadiene copolymer prepared in the above Examples and Comparative Examples and the molded article manufactured therefrom, tensile properties and viscoelastic properties were measured in the same manner as in Experiment #1, respectively. The results are shown in Table 5 below. Preparation of the molded product specimen was also prepared in the same manner as in Experiment #1.

* In the case of the index, the viscoelastic property is a value based on Comparative Example 2-1, and the workability property is a value based on Comparative Example 2-2.

As shown in Table 5, in Examples 2-1 and 2-2 using the modified conjugated diene polymer according to an embodiment of the present invention, while exhibiting excellent processability properties compared to Comparative Examples 2-1 to 2-5, It was confirmed that the tensile properties and viscoelastic properties were also excellent.

When comparing Examples 2-1 and 2-2 with Comparative Examples 2-1 to 2-3, it can be seen that a very remarkable difference in rotational resistance is shown and tensile properties are also improved, and Comparative Example 2- Compared to 4 and 2-5, it exhibited an improved viscoelastic property and remarkably improved processability properties while exhibiting tensile properties equal to or higher than those of 4 and 2-5, which is a structure in which a functional chain is bonded to the modifying agent by using the functional chain in the examples as a modification initiator. It can be seen that this is because it shows a very remarkable difference in workability because it is not.

Through this, the modified conjugated diene-based polymer of the present invention can exhibit a remarkable effect that is not expressed in Comparative Examples 2-4 and 2-5 by being prepared by a manufacturing method including the step of reacting with a functional chain after the denaturation reaction. Through this difference in effect, the modified conjugated diene-based polymer of the present invention has a different structure from the comparative examples, for example, a functional chain including a repeating unit derived from an N-functional group-containing monomer derived from a functional chain is modified. It can be predicted that the non-functional chain of the resulting polymer is coupled by a functional group derived from a modifier to form a structure similar to that of the graft copolymer.

Experiment #3

Manufacturing Example 3

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-4-methylenehexene-1-amine (N,N-dimethyl After adding -4-methylenehex-5-en-1-amine) (3 mole ratio to 1 mole of [act. Li]), it was reacted at 10° C. for 30 minutes to obtain a solution containing a functional chain (15.6 mmol/l). ) 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.

Example 3-1

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 30 minutes elapsed, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene. After 10 minutes elapsed, 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 and reacted for 15 minutes ([DTP]:[act. Li]=1.5:1 molar ratio, [denaturant]:[act. Li]=0.7:1 molar ratio). The solution containing the functional chain prepared in was added and reacted for 15 minutes ([act. Li]:[functional chain]=1:2 molar ratio), the reaction was stopped using ethanol, and the antioxidant Wingstay 33 g of a solution in which 30% by weight of K is dissolved in hexane was added, the resulting polymer was poured into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, and modified styrene- A butadiene copolymer was prepared.

Example 3-2

In Example 3-1, instead of 3,3'-(piperazin-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)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) Except for adding (N,N'-(cyclohexane-1,3-diyl(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) In the same manner as in Example 3-1, a modified styrene-butadiene copolymer was prepared ([modifier]:[act. Li]=0.7:1 molar ratio).

Comparative Example 3-1

In Example 3-1, a solution containing the functional chain prepared in Preparation Example 3 instead of n-butyllithium was added in an amount such that n-butyllithium of Example 3-1 and the functional chain were equimolar. The modified styrene-butadiene copolymer was carried out in the same manner as in Example 3-1, except that the reaction was stopped after capping butadiene without performing an adiabatic heating reaction, and then adding and reacting a denaturant and a functional chain. The coalescence was prepared.

Comparative Example 3-2

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 30 minutes elapsed, 39 g of 1,3-butadiene was added to cap the polymer end with butadiene. After 10 minutes elapsed, 3,3'-(piperazine-1,4-diyl)bis(N, N-bis(3-(triethoxysilyl)propyl)propan-1-amine) was added and reacted for 15 minutes ([DTP]:[act. Li]=1.5:1 molar ratio, [modifier]:[act] Li] = 0.7:1 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 3-3

In Comparative Example 3-2, a solution containing the functional chain prepared in Preparation Example 3 instead of n-butyllithium was added in an amount such that n-butyllithium of Comparative Example 3-2 and the functional chain became equimolar. A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 3-2, except that the adiabatic heating reaction was performed.

Evaluation of polymer properties

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 in the same manner as in Experiment #1, respectively. The results are shown in Table 6 below.

As shown in Table 6, in Examples 3-1 and 3-2, Si and N atoms were present in the polymer molecule, and it can be seen that the content of N atoms was significantly increased compared to Comparative Examples 3-1 and 3-2. .

Evaluation of properties of rubber molded products

In order to compare and analyze the physical properties of the rubber composition containing each modified styrene-butadiene copolymer prepared in the above Examples and Comparative Examples and the molded article manufactured therefrom, tensile properties and viscoelastic properties were measured in the same manner as in Experiment #1, respectively. The results are shown in Table 7 below. Preparation of the molded product specimen was also prepared in the same manner as in Experiment #1.

* All of the above indices are values based on Comparative Example 3-1.

As shown in Table 7, Examples 3-1 and 3-2 using the modified conjugated diene-based polymer according to an embodiment of the present invention exhibited excellent processability characteristics compared to Comparative Examples 3-1 to 3-3, while at the same time It was confirmed that the tensile properties and viscoelastic properties were also excellent.

When comparing Examples 3-1 and 3-2 with Comparative Examples 3-1 and 3-2, it was confirmed that a very remarkable difference was shown in rotational resistance and tensile properties were also improved, compared to Comparative Example 3-3. While exhibiting equal or higher tensile properties, improved viscoelastic properties and remarkably improved processability properties were exhibited.This is because the functional chain in the examples was used together with the modification initiator, and the functional chain was not bonded to the modifying agent. It can be seen that this is because there is a very remarkable difference.

Through this, it can be confirmed that the modified conjugated diene-based polymer of the present invention can exhibit a remarkable effect that is not expressed in Comparative Example 3-3 by being prepared by a manufacturing method comprising the step of reacting with a functional chain after the denaturation reaction. , Through this difference in effect, the modified conjugated diene-based polymer of the present invention is a copolymer having a structure different from Comparative Example 3-3, for example, a functional chain including a repeating unit derived from an N-functional group-containing monomer derived from a functional chain is modified. It can be predicted that the non-functional chain of the resulting polymer is coupled by a functional group derived from a modifier to form a structure similar to that of the graft copolymer.

Claims (10)

A unit derived from a modifier having 3 or more alkoxy groups bonded to silicon; A non-functional chain including a repeating unit derived from a conjugated diene-based monomer and forming a silicon-carbon bond at one side of the unit derived from the denaturant; And A modified conjugated diene-based polymer comprising a; a functional chain that forms a silicon-carbon bond at the other side of the unit derived from the modifier and includes at least two units derived from the monomer-containing N-functional group. 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 150 ppm or more based on weight. The method according to claim 1, The functional chain is a modified conjugated diene-based polymer that is bonded to one or more units derived from a denaturant. The method according to claim 1, The functional chain is a modified conjugated diene-based polymer further comprising a unit derived from a conjugated diene-based monomer. The method according to claim 1, The functional chain is a modified conjugated diene-based polymer containing from 2 to 80 units derived from an N-functional group-containing monomer. The method according to claim 1, The modifier is an amine-containing alkoxysilane-based compound or an amine-free alkoxysilane-based compound, and a modified conjugated diene-based polymer containing three or more alkoxysilane groups. The method according to claim 1, The non-functional chain is a modified conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl-based monomer. 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. A rubber composition comprising the modified conjugated diene polymer and a filler according to claim 1. The method of claim 9, 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.