KR20220033242A - Conjugaed diene-based elastomer and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a conjugated diene-based elastomer and a rubber composition comprising the same. The present invention provides the conjugated diene-based elastomer which comprises: a modified conjugated diene-based polymer; and a functional group-containing oligomer, wherein the functional group-containing oligomer comprises: a repeating unit derived from a compound represented by chemical formula 1; and a denaturant derived unit, wherein the denaturant is the compound comprising an aminoalkoxysilyl group or an alkoxysilyl group, and the rubber composition comprising the same.

Description

Conjugated diene-based elastomer and rubber composition comprising the same

The present invention relates to a conjugated diene-based elastomer having excellent processability, abrasion resistance and rotation resistance, and a rubber composition comprising the same.

Recently, as interest in energy saving and environmental issues increases, automobile fuel efficiency is required. As a rubber material for tires, it has low rolling resistance, excellent abrasion resistance and tensile properties, and also has adjustment stability typified by wet skid resistance. is being requested

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small tan δ and Goodrich heat generation is preferable.

As one of the methods for realizing this, a method of lowering the exothermicity of the tire by using an inorganic filler such as silica or carbon black in the rubber composition for forming a tire has been proposed, but this is because the inorganic filler in the rubber composition is not easily dispersed. Rather, there is a problem in that the physical properties of the rubber composition, including abrasion resistance, crack resistance, or processability, etc. are generally lowered.

In order to solve this problem, as a method for increasing the dispersibility of inorganic fillers such as silica or carbon black in the rubber composition, the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organic lithium can interact with the inorganic filler. Although a method of modifying with a modifier containing a functional group has been proposed, low heat generation is still improved, but there is a problem in that tensile properties, abrasion resistance, and workability are deteriorated.

JP, WO2013-077018, A1

The present invention has been devised to solve the problems of the prior art, and includes a modified conjugated diene-based polymer and a repeating unit derived from a compound represented by Formula 1; An object of the present invention is to provide a conjugated diene-based elastomer having excellent filler affinity by including a functional group-containing oligomer including a unit derived from a denaturant.

An object of the present invention is to provide a rubber composition excellent in workability, tensile properties, abrasion resistance and viscoelastic properties in a well-balanced manner, including the conjugated diene-based elastomer.

According to one embodiment of the present invention for solving the above problems, the present invention is a modified conjugated diene-based polymer; and a functional group-containing oligomer, wherein the functional group-containing oligomer includes a compound-derived repeating unit and a modifier-derived unit represented by the following formula (1), and the modifier is a compound containing an aminoalkoxysilyl group or an alkoxysilyl group. Provided is an elastomer based on:

[Formula 1]

In Formula 1,

R _11a and R _11b are each independently a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a single bond; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted 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 _11c is an alkyl group having 1 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; an aryl group having 6 to 20 carbon atoms; or a heterocyclic group having 3 to 20 carbon atoms;

R _11d to R _11g 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; an 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 present invention provides a rubber composition comprising the conjugated diene-based elastomer and a filler.

The conjugated diene-based elastomer according to the present invention includes a functional group-containing oligomer comprising a repeating unit derived from the compound represented by Formula 1 and a unit derived from a modifier including an aminoalkoxysilyl group or an alkoxysilyl group together with the modified conjugated diene-based polymer. It has excellent chemical properties and has an effect of improving processability, tensile properties, abrasion resistance and viscoelastic properties of a rubber composition containing the same in a balanced way.

Since the rubber composition according to the present invention contains the above-mentioned conjugated diene-based elastomer, the interaction between the rubber component and the filler is excellent, the polymer chain formation occurring between the fillers is suppressed, and the viscosity increase during processing can be suppressed, so that the processability is excellent. In addition, there is an excellent effect in balance between tensile properties, abrasion resistance and viscoelastic properties.

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

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Justice

As used herein, the term 'polymer' refers to a polymer compound prepared by polymerizing monomers, whether of the same or different type. The generic term polymer thus encompasses the terms homopolymer and copolymer, which are commonly used to refer to polymers prepared from only one monomer.

As used herein, the term 'oligomer chain' refers to an oligomer chain in which one or more monomers are polymerized so that monomer-derived units are repeatedly connected, and the number of repeats is several to several dozen, which means an oligomer chain with a relatively small molecular weight. there is.

As used herein, the term 'oligomer' may refer to an aggregate of oligomer chains including the oligomer chains.

As used herein, the term 'vinyl content' refers to the mass (or weight) of butadiene contained in positions 1 and 2 in the polymer chain, based on the portion (total amount of polymerized butadiene) of the conjugated diene monomer (butadiene, etc.) in the polymer. ) refers to the percentage.

As used herein, the term 'monovalent hydrocarbon group' refers to 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. and the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined according to the type of each substituent.

As used herein, the term 'divalent hydrocarbon group' refers to a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group including one or more unsaturated bonds, and an arylene group, such as carbon and hydrogen bonded 2 It may mean a valent atomic group, and the minimum number of carbon atoms of the substituent represented by the divalent hydrocarbon may be determined according to the type of each substituent.

As used herein, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl and isopropyl, sec-butyl, ter It may mean including all branched alkyl groups such as tert-butyl and neopentyl.

As used herein, the term 'alkenyl group' may refer to a monovalent aliphatic unsaturated hydrocarbon including one or two or more double bonds.

As used herein, the term 'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.

As used herein, the term 'alkylene group' may refer to a divalent aliphatic saturated 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 (polycyclic aromatic hydrocarbon) may be meant to include all of them.

As used herein, the term 'heterocyclic group' refers to a carbon atom in a cycloalkyl group or an aryl group in which one or more hetero atoms are substituted, for example, it may mean including both a heterocycloalkyl group or a heteroaryl group.

As used herein, the term 'single bond' may mean a single covalent bond itself that does not include a separate atom or molecular group.

The terms 'comprising', 'having' and their derivatives herein are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. . For the avoidance of any doubt, all compositions claimed through use of the term 'comprising', unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as 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' refers to the vinyl content in each polymer was measured and analyzed using Varian VNMRS 500 MHz NMR, and 1,1,2,2-tetrachloroethane was used as the solvent for NMR measurement. , the solvent peak is calculated as 6.0 ppm, 7.2-6.9 ppm is random styrene, 6.9-6.2 ppm is block styrene, 5.8-5.1 ppm is 1,4-vinyl and 1,2-vinyl, 5.1-4.5 ppm is 1, It is measured by calculating the content of 1,2-vinyl bonds 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 gel permeation chromatohraph (GPC) analysis, and measured by checking the molecular weight distribution curve. will be. Molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from each of the measured molecular weights. Specifically, the GPC uses a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC reference material (Standard material) is PS (polystyrene) The GPC measurement solvent is prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

In the present specification, the 'N atom content' may be measured through an NSX analysis method, and the NSX analysis method is measured using a trace nitrogen quantitative analyzer (NSX-2100H). Exemplarily, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar at 250 ml/min, O ₂ at 350 ml/min, ozonizer 300 ml/ Set the carrier gas flow rate to min, set the heater to 800°C, and wait for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, a calibration curve in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was prepared using Nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration was obtained. Then, draw a straight line using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample is placed on the auto sampler of the analyzer to obtain an area, and the N content is calculated using the area of the sample obtained and the calibration curve. At this time, the sample is a modified conjugated diene-based polymer in which the solvent is removed by putting it in hot water heated with steam and stirring, and the residual monomer, residual modifier, and oil are removed.

The present invention provides a conjugated diene-based elastomer that improves the processability, tensile properties, abrasion resistance, and viscoelastic properties of a rubber composition comprising the improved remarkably improved affinity with the filler by including the functional group-containing oligomer together with the modified conjugated diene-based polymer in a balanced manner provides

The conjugated diene-based elastomer according to an embodiment of the present invention may include a modified conjugated diene-based polymer; and a functional group-containing oligomer, wherein the functional group-containing oligomer includes a compound-derived repeating unit and a modifier-derived unit represented by the following formula (1), and the modifier is a compound comprising an aminoalkoxysilyl group or an alkoxysilyl group. .

[Formula 1]

In Formula 1,

R _11a and R _11b are each independently a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a single bond; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted 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 _11c is an alkyl group having 1 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; an aryl group having 6 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms,

R _11d to R _11g 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; an 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.

According to an embodiment of the present invention, the modified conjugated diene-based polymer is a homopolymer including a repeating unit derived from a conjugated diene-based monomer or a copolymer including a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer. can

In addition, the modified conjugated diene-based polymer may include a functional group derived from a modifier, whether the homopolymer or copolymer.

Here, the repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the repeating unit derived from the aromatic vinyl-based monomer may mean a repeating unit formed during polymerization of the aromatic vinyl-based monomer. , The functional group derived from the modifier is derived from a modifier present at at least one end of the active polymer through a reaction or coupling between a modifier and an active polymer prepared by polymerization of a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer It may mean a functional group.

According to an embodiment of the present invention, the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 It may be at least one selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom).

The aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1 It may be at least one selected from the group consisting of -vinyl-5-hexylnaphthalene.

In addition, when the modified conjugated diene-based polymer is a copolymer, the modified conjugated diene-based polymer may include an aromatic vinyl monomer-derived repeating unit in an amount of 30 wt% or more, or 30 wt% to 50 wt%, and rotation within this range There is an excellent balance between resistance and wet road resistance.

As another example, 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 repeating unit derived from the diene-based monomer 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 more than 0% by weight to 1% by weight of a repeating unit derived from the diene-based monomer, more than 0% by weight to 0.1% by weight, It may contain more than 0 wt% to 0.01 wt%, or more than 0 wt% to 0.001 wt%, and has the effect of preventing gel formation within this range.

According to an embodiment of the present invention, the copolymer may be a random copolymer, and in this case, an excellent balance between physical properties is obtained. The random copolymer may mean that repeating units constituting the copolymer are disorderly arranged.

In addition, the modified conjugated diene-based polymer may include a functional group including at least one of N and Si.

For example, the functional group may be an amino group, an amide group, an imino group, an imidazole group, a pyrimidyl group, a cyclic amino group, or a silyl group substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, and a carbon number A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroalkyl group having 2 to 20 carbon atoms including N, O or S, or N; It may be a heterocyclic group having 2 to 20 carbon atoms including O or S.

In another example, the functional group is an alkylamino group, an allylamino group, an alkylallylamino group, an alkylaminosilyl group, an alkylaminoalkylsilyl group, a trialkoxysilyl group, an alkylalkoxysilyl group, an alkylaminoalkoxysilyl group, a di(alkylsilyl)amino group or a di(alkylamino)silyl group.

In addition, the modified conjugated diene-based polymer may further include a ketone group, an epoxy group, an ether group, or an ester group in addition to a functional group including at least one of N and Si.

On the other hand, the functional group included in the modified conjugated diene-based polymer is a functional group derived from a modifier, and the modifier is a compound that can provide the above functional group among compounds applied as a modifier for the conjugated diene-based polymer. can be applied

In addition, the modified conjugated diene-based polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 100,000 g/mol to 3,000,000 g/mol, 200,000 g/mol to 2,000,000 g/mol Alternatively, it may be 300,000 g/mol to 1,500,000 g/mol, and within this range, driving resistance and wet road resistance are more balanced and excellent.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more and 2.0 or less, specifically 1.5 or more and 2.0 or less, and has excellent tensile properties and viscoelastic properties within this range, and each There is an excellent effect of the balance between the physical properties.

Meanwhile, the modified conjugated diene-based polymer may have 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.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a 1,2-vinyl bond content of 5 to 30% by weight based on the total weight of the polymer, and in this case, abrasion resistance and rotation resistance may be more excellent. .

On the other hand, the modified conjugated diene-based polymer according to an embodiment of the present invention can be prepared through a conventional batch-type or continuous polymerization method, for example, in a hydrocarbon solvent, in the presence of a polymerization initiator, a conjugated diene-based monomer or conjugated An active polymer may be prepared by batch- or continuous polymerization of a diene-based monomer and an aromatic vinyl-based monomer, and may be prepared by reacting the prepared active polymer with a modifier.

Here, the hydrocarbon solvent is not particularly limited, but may be, for example, at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene, and a polymerization initiator For example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naph tyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, 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 may be at least one selected from the group consisting of lithium isopropylamide.

In addition, the polymerization may be carried out by including a polar additive, and the polar additive is, for example, tetrahydrofuran, ditetrahydrofurylpropane, 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 and tetramethylethylenediamine It may be at least one selected from the group consisting of, preferably triethylamine or tetramethylethylenediamine. In this case, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in their reaction rate.

In addition, the functional group-containing oligomer according to an embodiment of the present invention may include a compound-derived repeating unit represented by Formula 1; and a unit derived from a modifier, wherein the modifier may be a compound containing an aminoalkoxysilyl group or an alkoxysilyl group.

In addition, the functional group-containing oligomer may have a structure in which oligomer chains including the compound-derived repeating unit represented by Formula 1 are coupled by the modifier-derived unit.

Specifically, the functional group-containing oligomer is prepared by polymerizing the compound represented by Formula 1 in the presence of a polymerization initiator in a hydrocarbon solvent to prepare an active oligomer having a low molecular weight including a repeating unit derived from the compound represented by Formula 1, and a denaturant It may be prepared by reacting, whereby one end of the active oligomer is bonded to a silyl group in the molecule of the modifier through a substitution reaction between the anion active site located at one end of the active oligomer and the alkoxy group of the modifier. It may have a structure.

On the other hand, the oligomer chain may further include a repeating unit derived from a conjugated diene-based monomer. In this case, the functional group-containing oligomer is obtained by polymerizing the compound represented by Formula 1 and the conjugated diene-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator. It may be prepared by preparing an active oligomer and reacting it with a denaturant.

At this time, the number of active oligomers binding to the silyl group in the denaturant molecule can be controlled by adjusting the ratio of the denaturant during the reaction between the active oligomer and the denaturant. The ratio of the denaturant is not particularly limited, but at least two active oligomers per molecule of the denaturant are not particularly limited. While binding, the weight average molecular weight of the functional group-containing oligomer may be adjusted to a range to be within the range to be described later.

The functional group-containing oligomer has a weight average molecular weight of 50,000 g/mol or less, specifically 1,000 g/mol or more and 50,000 g/mol or less, 1,000 g/mol or more and 30,000 g/mol or less, or 1,000 g/mol or more and 20,000 g/mol may be below. In this case, the filler affinity of the conjugated diene-based elastomer including the same may be more excellent, and as a result, there is an effect of excellent mechanical properties such as tensile properties and viscoelastic properties of the rubber composition including the same.

In addition, the conjugated diene-based elastomer according to an embodiment of the present invention may include the functional group-containing oligomer in an amount of 10 parts by weight or less, or 0.001 parts by weight or more and 4 parts by weight or less, based on 100 parts by weight of the modified conjugated diene-based polymer. In this case, the filler affinity of the conjugated diene-based elastomer may be further improved, and the rotational resistance property of the rubber composition including the conjugated diene-based elastomer may be improved.

Meanwhile, in Formula 1, R _11a and R _11b are each independently a single bond or an unsubstituted C 1 to C 10 alkylene group, R _11c is a C 1 to C 10 alkyl group, R _11d to R _{11 g} are each independently into an alkyl group having 1 to 10 carbon atoms; Or it may be a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

As another example, in Formula 1, R _11a and R _11b are each independently a single bond or an unsubstituted C 1 to C 6 alkylene group, R _11c is an alkyl group having 1 to 6 carbon atoms, and R _11d to R _{11 g} are each other independently an alkyl group having 1 to 6 carbon atoms; Or it may be a trialkylsilyl group substituted with an alkyl group having 1 to 6 carbon atoms.

More specifically, the compound represented by Formula 1 may be at least one selected from compounds represented by Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formula 1-3, Me is a methyl group.

In addition, the compound including an aminoalkoxysilyl group among the modifiers may be exemplarily a compound represented by the following formula (2).

[Formula 2]

In Formula 2, 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 is hydrogen, an epoxy group, or an alkylene group having 1 to 10 carbon atoms. It may be a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R ²¹ may be a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, and a and m are each independently from 1 to 3 It may be an integer selected from, n may be an integer from 0 to 2, and j may be an integer selected from 1 to 30.

As a specific example, the compound represented by Formula 2 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 (trimethoxysilyl)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) Propyl)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)prop 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-pentaoxahexadecan-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine) may be one selected from the group consisting of.

As another example, the compound represented by Formula 2 may be at least one selected from compounds represented by Formulas 2-1 to 2-6 below.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]]

[Formula 2-5]

[Formula 2-6]

In Formulas 2-1 to 2-6, Me is a methyl group, and Et is an ethyl group.

As another example, the compound including an aminoalkoxysilyl group among the modifiers may include a compound represented by the following formula (3).

[Formula 3]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.In Formula 3, 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 are each independently an alkyl group having 1 to 10 carbon atoms. may be, R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 1, 2 or 3, and may be b+c≥4, and A is

or

may be, and 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 3 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 compound including an aminoalkoxysilyl group among the modifiers may include a compound represented by Formula 4 below.

[Formula 4]

In Formula 4, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms including or not including an oxygen atom, and R ¹⁷ to R ²⁰ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. may be a hydrocarbon group, and L ¹ to L ⁴ are each independently a monosubstituted, disubstituted or trisubstituted 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, a ring formed may include 1 to 3 at least one hetero atom selected from the group consisting of N, O and S.

As a specific example, the compound represented by Formula 4 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-diethylmethan-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 Toxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-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-dipropylmethan-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-dimethylmethan-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-dipropylmethan-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-tetraprotoxy) 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).

More specifically, the compound represented by Chemical Formula 4 may be a compound represented by the following Chemical Formula 4-1.

[Formula 4-1]

In Formula 4-1, Me is a methyl group.

As another example, the compound including an aminoalkoxysilyl group among the modifiers may include a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, 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 each independently a carbon number 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.

Specifically, the compound represented by the formula (5) may be a compound represented by the following formula (5-1).

[Formula 5-1]

In Formula 5-1, Et is an ethyl group.

As another example, the compound including an aminoalkoxysilyl group among the modifiers may include a compound represented by the following formula (6).

[Formula 6]

In Formula 6, R _e1 and R _e2 are each independently an alkylene group having 1 to 10 carbon atoms, and _Re3 to R _e6 are 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 _Re3 to _Re6 is —R _e7 SiR _e8 Re9 _{Re9 Re10} , wherein _Re7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and _Re8 to _Re10 are independently of each other 1 carbon number an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein at least one of R _e8 to R _e10 is an alkoxy group having 1 to 10 carbon atoms.

Specifically, the compound represented by Chemical Formula 6 may be a compound represented by the following Chemical Formula 6-1.

[Formula 6-1]

In Formula 6-1, Me is a methyl group.

As another example, the compound including an aminoalkoxysilyl group among the modifiers may include a compound represented by the following formula (7).

[Formula 7]

In Formula 7, 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, 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. am.

Specifically, the compound represented by Formula 7 may be a compound represented by Formula 7-1 or Formula 7-2.

[Formula 7-1]

[Formula 7-2]

In Formulas 7-1 and 7-2, Me is a methyl group.

As another example, the compound including an alkoxysilyl group among the modifiers may include a compound represented by the following Chemical Formula 8.

[Formula 8]

In Formula 8, X is O or S, 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, and 1 to 10 carbon atoms of an alkyl group, 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 0 or an integer of 1, and when p is 0 R _f1 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

Specifically, the compound represented by Formula 8 may be a compound represented by Formula 8-1 or Formula 8-2.

[Formula 8-1]

[Formula 8-2]

As another example, the compound including an alkoxysilyl group among the modifiers may include a compound represented by the following Chemical Formula 9.

[Formula 9]

In Formula 9, 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 Si(OR _g6)r (R _g7 ) _3-r , wherein at least one of R _g1 to R _g4 is -R _g5 Si(OR _g6)r (R _g7 ) _3-r , wherein R _g5 is a single bond or an alkylene group having 1 to 10 carbon atoms. and R _g6 and R _g7 are each independently an alkyl group having 1 to 10 carbon atoms, r is 1 to 3, Y is C or N, but when Y is N, R _g4 is not present.

Specifically, the compound represented by Chemical Formula 9 may be a compound represented by the following Chemical Formula 9-1.

[Formula 9-1]

In Formula 9-1, Me is a methyl group.

As another example, the compound including an alkoxysilyl group among the modifiers may include a compound represented by the following Chemical Formula 10.

[Formula 10]

In Formula 10, 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 from 2 to 100 .

Specifically, in Formula 10, R _g1 to R _g3 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R _g4 is an alkoxy group having 1 to 6 carbon atoms, and q is 2 to 50 is the integer of

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

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 the filler based on 100 parts by weight of the conjugated diene-based elastomer. The filler may be, for example, a silica-based filler or a carbon black-based filler, and specific examples thereof include wet silica (hydrous silicic acid), fumed silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably fracture properties. It may be the wet silica which has the best effect of improving the effect and wet grip.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation may be used together, and in 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 It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, the rubber composition according to an embodiment of the present invention includes a modified conjugated diene-based polymer in which a functional group with high affinity for silica is introduced as a rubber component in the active site and contains a functional group-containing oligomer, so silane The blending amount of the coupling agent may be reduced than in the usual 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, within this range. There is an effect of preventing gelation of the rubber component while sufficiently exhibiting the effect as a coupling agent in the interior.

In addition, the rubber composition may further include other rubber components in addition to the modified conjugated diene-based polymer as needed, wherein the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. 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 in the conjugated diene-based elastomer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined of 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, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, and within this range, the vulcanized rubber composition has a low fuel efficiency while securing the required elastic modulus and strength. It has an excellent effect.

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

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), 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. Naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant 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 condensate of diphenylamine and acetone, etc., may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the compounding prescription, 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 may include each member of the tire, such as a tire tread, under tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, chaff, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

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, in order to describe the present invention in detail, examples will be described in detail. However, the embodiment 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 embodiment described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1

1) Manufacture of modified conjugated diene-based polymer

After putting 215 g of styrene, 765 g of 1,3-butadiene, 5000 g of n-hexane and 2,2-di(2-tetrahydrofuryl)propane as a polar additive in a 20 L autoclave reactor, the temperature inside the reactor was increased to 40°C. The temperature was raised. When the internal temperature of the reactor reached 40 °C, 4.3 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. After 20 extra lapses, 20 g of 1,3-butadiene was added, and the end of the polymer chain was capped with butadiene. After 5 minutes, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine) was added as a denaturant for 15 minutes. reacted (denaturant:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in 0.3 wt% in n-hexane was added to prepare a polymer solution containing a modified conjugated diene-based polymer.

2) Preparation of functional group-containing oligomers

20 g, 1, N,N,N',N',1-pentamethyl-1-vinylsilanediamine (N,N,N'.N',1-pentamethyl-1-vinylsilanediamine) in a 2 L autoclave reactor 100 g of 3-butadiene, 500 g of n-hexane, and 2,2-di(2-tetrahydrofuryl)propane as a polar additive were added, and then the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 20 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. N,N'-(Cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as modifier )(N,N'-(cyclohexane-1,3-diyl(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) was added and reacted for 15 minutes (Molar ratio of denaturant: act. Li = 0.7:1) After stopping the polymerization reaction using ethanol, 5 ml of a solution in which an antioxidant IR1520 (BASF Corporation) is dissolved in 0.3 wt% in n-hexane was added to give a functional group An oligomer solution containing the containing oligomer was prepared.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 2

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

N,N'-(Cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as modifier ) instead of 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) to prepare an oligomer solution containing a functional group-containing oligomer (modifier:act. Li=0.7:1 molar ratio).

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 3

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

N,N,N',N'-tetramethyl-1-methyl-1-vinylsilanediamine (N,N,N',N'-tetramethyl-1-methyl-1-vinylsilanediamine) 20 in a 2 L autoclave reactor g, 100 g of 1,3-butadiene, 500 g of n-hexane, and 2,2-di(2-tetrahydrofuryl)propane as a polar additive were added, and then the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 50 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacilidine(2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1 as modifier ,2-azasilolidine) was added and reacted for 15 minutes (denaturant:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution containing an antioxidant IR1520 (BASF) dissolved in 0.3 wt% in n-hexane was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 4

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

3,3'-(1,1,3,3-tetramethoxydiol instead of 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacilidine as denaturant Siloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3′-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N -diethylpropan-1-amine) was added, and an oligomer solution containing a functional group-containing oligomer was prepared in the same manner as in Example 1 (denaturant:act. Li=0.7:1 molar ratio).

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 5

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

1-Methyl-N,N,N',N'-tetrakis(trimethylsilyl)-1-vinylsilanediamine (1-methyl-N,N,N',N'-tetrakis(trimethylsilyl) in a 2 L autoclave reactor )-1-vinylsilanediamine) 20 g, 1,3-butadiene 100 g, n-hexane 500 g, and 2,2-di(2-tetrahydrofuryl) propane as a polar additive were added, and the temperature inside the reactor was adjusted to 40°C. did When the internal temperature of the reactor reached 40 °C, 50 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. 3,3'-(piperazin-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 (denaturant:act. Li=0.7:1 molar ratio), followed by ethanol to stop the polymerization reaction, and 5 ml of a solution containing an antioxidant IR1520 (BASF) dissolved in 0.3 wt% in n-hexane was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 6

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

N,N-diethyl- instead of 3,3'-(piperazin-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine) as denaturant A functional group-containing oligomer was included in the same manner as in Example 1, except that 3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine) was added. oligomer solution was prepared (denaturant:act. Li=0.7:1 molar ratio).

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 7

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

N,N'-(Cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as modifier ), an oligomer solution containing a functional group-containing oligomer was prepared in the same manner as in Example 1 except that tetramethoxysilane was added instead (modifier:act. Li=0.7:1 molar ratio).

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 8

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

N,N'-(Cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine as modifier ), an oligomer solution containing a functional group-containing oligomer was prepared in the same manner as in Example 1 except that hexamethoxydisiloxane was added instead (denaturant: act. Li=0.7:1 molar ratio).

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 9

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

3,3,7,7-tetramethoxy-5,5 instead of 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacilidine as denaturant -bis((trimethoxysilyl)methyl)-2,8-dioxa-3,7-disilanonan(3,3,7,7-tetramethoxy-5,5-bis((trimethoxysilyl)methyl-2, An oligomer solution including a functional group-containing oligomer was prepared in the same manner as in Example 1, except that 8-dioxa-3,7-disilanonane) was added (denaturant:act. Li=0.7:1 molar ratio).

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 10

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 3.

2) Preparation of functional group-containing oligomers

20 mmol of n-butyllithium was added, and tetramethoxysilane was added instead of 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azacilidine as a modifier. An oligomer solution including a functional group-containing oligomer was prepared in the same manner as in Example 3 except for the above (modifier:act. Li=0.7:1 molar ratio).

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 11

A conjugated diene-based elastomer was prepared in the same manner as in Example 7, except that the functional group-containing oligomer solution was used in a ratio such that the functional group-containing oligomer solid content was 5 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solid content.

Comparative Example 1

After putting 215 g of styrene, 765 g of 1,3-butadiene, 5000 g of n-hexane and 2,2-di(2-tetrahydrofuryl)propane as a polar additive in a 20 L autoclave reactor, the temperature inside the reactor was increased to 40°C. The temperature was raised. When the internal temperature of the reactor reached 40 °C, 4.3 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. After 20 extra lapses, 20 g of 1,3-butadiene was added, and the end of the polymer chain was capped with butadiene. After 5 minutes, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a modifier was added and reacted for 15 minutes (modifier:act. Li=0.7:1 molar ratio). was added and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane in an amount of 0.3 wt% was added. The resulting polymer was put into hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene-based polymer.

Comparative Example 2

1) Preparation of first modified conjugated diene-based polymer

A modified conjugated diene-based polymer solution prepared in the same manner as in 1) of Example 1 was prepared, and this was used as the first modified conjugated diene-based polymer solution.

2) Preparation of the second modified conjugated diene-based polymer

In a 2 L autoclave reactor, 20 g of styrene, 100 g of 1,3-butadiene, 500 g of n-hexane, and 2,2-di(2-tetrahydrofuryl)propane were put as a polar additive, and then the temperature inside the reactor was increased to 40°C. adjusted. When the internal temperature of the reactor reached 40 °C, 4 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. Tetramethoxysilane was added as a modifier and reacted for 15 minutes (modifier:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which an antioxidant IR1520 (BASF Corporation) was dissolved in 0.3 wt% of n-hexane was added to the second modified conjugated diene containing the second modified conjugated diene-based polymer. A polymer solution was prepared.

3) Preparation of conjugated diene-based elastomer

A mixed polymer is obtained by mixing the first modified conjugated diene-based polymer solution prepared in 1) with the second modified conjugated diene-based polymer solution prepared in 2), and the obtained polymer is placed in hot water heated with steam and stirred to obtain a solvent. It was removed to prepare a conjugated diene-based elastomer. In this case, the second modified conjugated diene-based polymer solution is mixed so that the solid content of the second modified conjugated diene-based polymer in the solution is 1.0 parts by weight based on 100 parts by weight of the solid content of the first modified conjugated diene-based polymer in the first modified conjugated diene-based polymer solution. did

Reference Example 1

1) Preparation of first modified conjugated diene-based polymer

A modified conjugated diene-based polymer solution prepared in the same manner as in 1) of Example 1 was prepared, and this was used as the first modified conjugated diene-based polymer solution.

2) Preparation of functional group-containing oligomers

1-Methyl-N,N,N',N'-tetrakis(trimethylsilyl)-1-vinylsilanediamine (1-methyl-N,N,N',N'-tetrakis(trimethylsilyl) in a 2 L autoclave reactor )-1-vinylsilanediamine) 20 g, 1,3-butadiene 100 g, n-hexane 500 g, and 2,2-di(2-tetrahydrofuryl) propane as a polar additive were added, and the temperature inside the reactor was adjusted to 40°C. did. When the internal temperature of the reactor reached 40 °C, 40 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. N,N-diethyl-3-(trimethoxysilyl)propan-1-amine was added as a modifier and reacted for 15 minutes (modifier:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Reference Example 2

A conjugated diene-based elastomer was prepared in the same manner as in Reference Example 1, except that the functional group-containing oligomer solution was used in a proportion such that the functional group-containing oligomer solid content was 20 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solid content.

Reference Example 3

1) Preparation of first modified conjugated diene-based polymer

A modified conjugated diene-based polymer solution prepared in the same manner as in 1) of Example 1 was prepared, and this was used as the first modified conjugated diene-based polymer solution.

2) Preparation of functional group-containing oligomers

In a 2L autoclave reactor, 20 g of N,N,N',N',1-pentamethyl-1-vinylsilanediamine, 100 g of 1,3-butadiene, 500 g of n-hexane and 2,2-diamine as a polar additive After (2-tetrahydrofuryl) propane was added, the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 5 mmol of n-butyllithium was added to proceed with adiabatic temperature increase. Tetramethoxysilane was added as a modifier and reacted for 15 minutes (modifier:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Reference Example 4

A conjugated diene-based elastomer was prepared in the same manner as in Example 7, except that the functional group-containing oligomer solution was used in a ratio such that the functional group-containing oligomer solid content was 20 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solid content.

Experimental Example 1

The physical properties of each of the conjugated diene-based elastomers (in Comparative Example 1, meaning a modified conjugated diene-based polymer) prepared in Examples 1 to 11, Comparative Examples 1, 2 and Reference Examples 1 to 4 were comparatively analyzed, and the results are shown in Tables 1 and 2 below.

1) Weight average molecular weight (Mw, g/mol)

The weight average molecular weight of each functional group-containing oligomer and the second modified conjugated diene-based polymer was measured through gel permeation chromatohraph (GPC) analysis. The GPC is a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC standard material (Standard material) is PS (polystyrene). The GPC measurement solvent was prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

2) N content

The N content in each conjugated diene-based elastomer was measured through the NSX analysis method. For NSX analysis, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) using a trace nitrogen quantitative analyzer (NSX-2100H), Ar 250 ml/min, O ₂ 350 ml/min, ozonizer 300 Set the carrier gas flow rate to ml/min, set the heater to 800°C, wait for about 3 hours to stabilize the analyzer, and after stabilizing the analyzer, use Nitrogen standard (AccuStandard S-22750-01-5 ml) A calibration curve was drawn in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and after obtaining the area corresponding to each concentration, a straight line was drawn using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample was placed on the auto sampler of the analyzer to obtain an area, and the N content was calculated using the area of the obtained sample and the calibration curve.

division Weight average molecular weight (Mw, g/mol) N atom content (ppm) Functional group-containing oligomers Second modified conjugated diene-based polymer Conjugated diene-based elastomer Example 1 23860 - 375 Example 2 18050 - 399 Example 3 7320 - 312 Example 4 6120 - 341 Example 5 12100 - 293 Example 6 5940 - 219 Comparative Example 1 - - 75 Comparative Example 2 - 95800 75 Reference Example 1 63158 - 197 Reference Example 2 63200 - 2875

division Weight average molecular weight (Mw, g/mol) N atom content (ppm) Functional group-containing oligomers Second modified conjugated diene-based polymer Conjugated diene-based elastomer Example 7 18300 - 365 Example 8 31300 - 361 Example 9 35500 - 339 Example 10 17900 - 289 Example 11 18300 - 1525 Comparative Example 1 - - 75 Comparative Example 2 - 95800 75 Reference Example 3 72300 - 368 Reference Example 4 18300 - 5875

As shown in Tables 1 and 2, the conjugated diene-based elastomers of Examples 1 to 11 contained 100 ppm or more of N atoms, and a functional group having a weight average molecular weight of 50,000 g/mol or less together with the modified conjugated diene-based polymer. containing oligomers were included.

On the other hand, Examples 1 to 11 each significantly increased the N atom content compared to Comparative Example 1, and through this, it can be predicted that the functional group-containing oligomer presented in the present invention is present in each conjugated diene-based elastomer.

Example 12

100 parts by weight of the conjugated diene-based elastomer prepared in Example 1, 70 parts by weight of silica, 11.2 parts by weight of an organosilane coupling agent (X50S, Evonik), 37.5 parts by weight of TDAE oil, 3 parts by weight of a zincating agent (ZnO) parts, 2 parts by weight of stearic acid, 2 parts by weight of an antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), 2 parts by weight of an antioxidant (6PPD ((dimethylbutyl)-N-phenyl) -Phenylenediamine) 2 parts by weight and wax (Microcrystaline Wax) 1 part by weight were kneaded.At this time, the initial temperature was controlled to 70° C., and after the mixing was completed, a primary formulation was obtained at a discharge temperature of 145° C. to 155° C. , After cooling the first formulation to room temperature, 1.5 parts by weight of sulfur powder, 1.75 parts by weight of a rubber accelerator (DPG (diphenylguanidine)) and a vulcanization accelerator (CZ (N-cythlohexyl-2-benzothiazylsulfenamide) )) was added and 2 parts by weight was added and mixed at a temperature of 100° C. or less to obtain a secondary formulation, followed by a curing process at 160° C. for 20 minutes to prepare a rubber specimen.

Examples 13 to 22

In Example 12, instead of 100 parts by weight of the conjugated diene-based elastomer prepared in Example 1, 100 parts by weight of each of the conjugated diene-based elastomers prepared in Examples 2 to 11 were used in the same manner except that 100 parts by weight of the conjugated diene-based elastomer was used. And to obtain a secondary formulation, finally a rubber specimen was prepared.

Comparative Examples 3 and 4

In Example 12, the modified conjugated diene-based polymer of Comparative Example 1 and 100 parts by weight of the conjugated diene-based elastomer of Comparative Example 2 were used instead of 100 parts by weight of the conjugated diene-based elastomer prepared in Example 1, except that 100 parts by weight of the conjugated diene-based elastomer was used. to obtain a first compound and a secondary compound, and finally, a rubber specimen was prepared.

Reference Examples 5 to 8

In Example 12, the first formulation and the second formulation were performed in the same manner except that 100 parts by weight of the conjugated diene-based elastomer of Reference Examples 1 to 4 was used instead of 100 parts by weight of the conjugated diene-based elastomer prepared in Example 1. was obtained and finally a rubber specimen was prepared.

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions prepared in Examples, Comparative Examples and Reference Examples, tensile properties, viscoelastic properties, abrasion resistance and processability properties were measured, and the results are shown in Tables 3 and 4 below.

1) 300% modulus

Each test piece was prepared according to the test method of ASTM D6746, and the tensile stress (300% modulus) at the time of 300% elongation of the test piece was measured. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester.

2) Viscoelastic properties

For the 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°C to 60°C) in Film Tension mode using a dynamic mechanical analyzer (GABO). At this time, the lower the high temperature 60 ℃ tan δ value, the less the hysteresis loss and the better the rotation resistance (fuel efficiency). indicates excellence.

3) Wear resistance

For each rubber specimen, a DIN abrasion test was performed in accordance with ASTM D5963, and a DIN loss index (loss volume indes): ARIA (Abration resistance index, Method A) based on the measured value of Comparative Example 3 The higher the number, the better.

4) Machinability characteristics

1) Mooney viscosity (MV, (ML1+4, @100℃ MU)) of the primary compound obtained during the manufacture of 1) rubber specimen was measured and the processability characteristics of each polymer were comparatively analyzed. Although the characteristics are excellent, in Tables 3 and 4 below, since the measured values of Comparative Example 3 were indexed on the basis of 100, the higher the value, the better.

Specifically, using MV-2000 (ALPHA Technologies) at 100°C, using a Rotor Speed of 2±0.02 rpm, and a Large Rotor, each primary formulation was left at room temperature (23±3°C) for at least 30 minutes and then 27 ±3 g was collected and filled inside the die cavity, and the platen was operated for 4 minutes.

division 300% modulus
(kgf/cm ² ) tan δ at 60℃ Machinability characteristics wear resistance Example 12 154 121 99 119 Example 13 157 123 105 124 Example 14 155 116 100 118 Example 15 154 118 98 119 Example 16 156 115 103 117 Example 17 160 113 97 116 Comparative Example 3 145 100 100 100 Comparative Example 4 130 95 95 112 Reference Example 5 156 102 87 105 Reference Example 6 168 112 86 85

division 300% modulus
(kgf/cm ² ) tan δ at 60℃ Machinability characteristics wear resistance Example 18 164 111 103 117 Example 19 164 112 103 117 Example 20 161 107 107 118 Example 21 159 105 110 119 Example 22 168 115 100 115 Comparative Example 3 145 100 100 100 Comparative Example 4 130 95 95 112 Reference Example 7 148 109 88 105 Reference Example 8 172 108 85 88

As shown in Tables 3 and 4, in Examples 12 to 22, compared to Comparative Examples 3 and 4, the tensile properties, viscoelastic properties, abrasion resistance and workability properties were improved in a balanced way.

Specifically, Examples 12 to 22 have a 300% modulus of about 6% to 16%, and a rotation resistance (tan δ at 60°C) of 5% to 23%, and The abrasion resistance exhibited a significantly increased effect of 15% to 24%, and compared to Comparative Example 4, the 300% modulus was about 18% to 26%, and the rotational resistance (tan δ at 60° C.) ) showed a greatly improved effect of about 11% to 29%, and abrasion resistance up to about 11%. Here, Comparative Examples 3 and 4 do not include the functional group-containing oligomer presented in the present invention, and in particular, Comparative Example 4 includes two modified conjugated diene-based polymers other than the functional group-containing oligomer presented in the present invention. will do

In addition, Examples 12 to 22 showed improved rotation resistance and 300% modulus compared to Reference Examples 5 to 8, respectively, and particularly showed significantly improved effects in processability characteristics and wear resistance, and Examples 12 to 22 were Reference Example 5 It was confirmed that the measured tensile properties, viscoelastic properties, abrasion resistance and workability properties were all well-balanced compared to 8 to 8. Here, each of Reference Examples 5 to 8 includes a functional group-containing oligomer, but includes a functional group-containing oligomer having a weight average molecular weight of more than 50,000 g/mol, or a functional group-containing oligomer modified conjugated diene-based polymer 100 parts by weight It is included in excess of 10 parts by weight.

The results of Tables 3 and 4 show that the conjugated diene-based elastomer according to the present invention includes a repeating unit derived from the compound represented by Formula 1 together with the modified conjugated diene-based polymer, and a modifier-derived unit comprising an aminoalkoxysilyl group or an alkoxysilyl group. By including it, it is excellent in filler affinity, and it means that there is an effect of improving the processability, tensile properties, abrasion resistance and viscoelastic properties of a rubber composition including the same in a balanced way. In addition, the conjugated diene-based elastomer according to the present invention includes the functional group-containing oligomer having an average molecular weight of 50,000 g/mol or less in a specific content or less, and contains N atoms in a specific content or more with respect to the total weight of the elastomer, so that the above effect is further improved it can be confirmed that

Claims (13)

modified conjugated diene-based polymers; and
It contains a functional group-containing oligomer,
The functional group-containing oligomer includes a compound-derived repeating unit and a modifier-derived unit represented by the following formula (1),
The modifier is a conjugated diene-based elastomer that is a compound containing an aminoalkoxysilyl group or an alkoxysilyl group:
[Formula 1]

In Formula 1,
R _11a and R _11b are each independently a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a single bond; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted 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 _11c is an alkyl group having 1 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; an aryl group having 6 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms,
R _11d to R _11g 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; an 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.
According to claim 1,
In Formula 1,
R _11a and R _11b are each independently a single bond or an unsubstituted C 1 to C 10 alkylene group,
R _11c is an alkyl group having 1 to 10 carbon atoms,
R _11d to R _11g are each independently an alkyl group having 1 to 10 carbon atoms; Or a conjugated diene-based elastomer that is a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.
According to claim 1,
In Formula 1,
R _11a and R _11b are each independently a single bond or an unsubstituted C 1 to C 6 alkylene group,
R _11c is an alkyl group having 1 to 6 carbon atoms,
R _11d to R _11g are each independently an alkyl group having 1 to 6 carbon atoms; Or a conjugated diene-based elastomer that is a trialkylsilyl group substituted with an alkyl group having 1 to 6 carbon atoms.
According to claim 1,
100 parts by weight of a modified conjugated diene-based polymer; and 10 parts by weight or less of the functional group-containing oligomer.
According to claim 1,
A conjugated diene-based elastomer having an N atom content of 100 ppm or more based on the total weight of the conjugated diene-based elastomer.
According to claim 1,
The functional group-containing oligomer is a conjugated diene-based elastomer having a weight average molecular weight of 50,000 g/mol or less.
According to claim 1,
The functional group-containing oligomer is a conjugated diene-based elastomer in which oligomer chains including a repeating unit derived from the compound represented by Formula 1 are coupled by a denaturant-derived unit.
8. The method of claim 7,
The oligomer chain is a conjugated diene-based elastomer further comprising a repeating unit derived from a conjugated diene-based monomer.
According to claim 1,
The modified conjugated diene-based polymer is a homopolymer comprising a repeating unit derived from a conjugated diene-based monomer or a copolymer comprising a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer.
According to claim 1,
The modified conjugated diene-based polymer is a conjugated diene-based elastomer comprising a functional group including at least one of N and Si.
A rubber composition comprising the conjugated diene-based elastomer of claim 1 and a filler.
12. The method of claim 11,
The filler is a silica-based filler or a carbon black-based filler in a rubber composition.
12. The method of claim 11,
A rubber composition comprising 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the conjugated diene-based elastomer.