KR20210033413A - Modified conjugated diene-based polymer, preparing method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer having excellent processability, excellent tensile strength and viscoelastic properties, and a rubber composition comprising the same. The present invention provides a modified conjugated diene-based polymer, which comprises: a polymer chain including a repeating unit derived from a conjugated diene-based monomer; a functional group derived from a modified oligomer bonded to one end of the polymer chain; and a functional group derived from an aminoalkoxysilane-based modifier containing an amine group and an alkoxysilyl group bonded to the other end of the polymer chain. And the present invention provides a modified conjugated diene-based polymer, in which the modified oligomer includes at least two oligomer chains including a repeating unit derived from an N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer, a unit derived from a silyl group-containing coupling agent, and a unit derived from an organometallic compound, and each of the oligomer chains is bonded through the unit derived from the silyl group-containing coupling agent.

Description

Modified conjugated diene-based polymer, a method for producing the same, and a rubber composition comprising the same TECHNICAL FIELD {MODIFIED CONJUGATED DIENE-BASED POLYMER, PREPARING METHOD THEREOF AND RUBBER COMPOSITION COMPRISING THE SAME}

The present invention relates to a modified conjugated diene polymer having excellent processability and rolling resistance properties, a method for preparing the same, 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.

US 4397994 A

The present invention was devised to solve the problems of the prior art, and an object of the present invention is to provide a modified conjugated diene-based polymer having excellent affinity with a filler and excellent processability and rolling resistance properties.

In addition, an object of the present invention is to provide a method for preparing the 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 polymer chain comprising a repeating unit derived from a conjugated diene-based monomer; A functional group derived from a modified oligomer bonded to one end of the polymer chain; And a functional group derived from an aminoalkoxysilane modifier containing an amine group and an alkoxysilyl group bonded to the other end of the polymer chain, wherein the modified oligomer comprises a repeating unit derived from a compound containing an N-functional group and a repeating unit derived from a conjugated diene monomer. At least two oligomer chains, a unit derived from a silyl group-containing coupling agent, and a unit derived from an organometallic compound, wherein each of the oligomer chains comprises a first modified oligomer bonded to each other through the unit derived from the silyl group-containing coupling agent. It provides a modified conjugated diene-based polymer containing.

In addition, the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a modified oligomer (S1); And reacting the active polymer with an aminoalkoxysilane modifier containing an amine group and an alkoxysilyl group (S2), wherein the modified oligomer comprises a repeating unit derived from a compound containing an N-functional group and a repeating unit derived from a conjugated diene monomer. At least two oligomer chains, a unit derived from a silyl group-containing coupling agent, and a unit derived from an organometallic compound, wherein each of the oligomer chains comprises a first modified oligomer bonded to each other through the unit derived from the silyl group-containing coupling agent. It provides a method for producing the modified conjugated diene-based polymer of claim 1, including.

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

The modified conjugated diene-based polymer according to the present invention includes an oligomer chain including a repeating unit derived from an N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer, and a unit derived from a silyl group-containing coupling agent, wherein the oligomer chain contains a silyl group. Excellent affinity with a filler by including a functional group derived from a modified oligomer including a first modified oligomer having a branched structure coupled with a unit derived from a coupling agent at one end and a functional group derived from a denaturant at the other end. Therefore, it has excellent blending processability and excellent rolling resistance.

The method for preparing a modified conjugated diene-based polymer according to the present invention includes preparing an active polymer in the presence of the modified oligomer and reacting with a modifying agent, so that the modified conjugated diene-based polymer can be easily prepared.

In addition, the rubber composition according to the present invention may have excellent rolling resistance characteristics and at the same time excellent processability characteristics 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.

Justice

In the present invention, the term'polymer chain' refers to a polymer chain in which monomer-derived units are repeatedly linked by polymerization of one or more monomers, but may refer to a high polymer chain having a large molecular weight with a number of repetitions of several hundred or more. .

In the present invention, the term'polymer' may mean an aggregate of polymer chains including the polymer chains described above.

In the present invention, the term'oligomer chain' refers to an oligomer chain in which monomer-derived units are repeatedly linked by polymerization of one or more monomers, but the number of repetitions is several to tens, and the molecular weight is relatively small. have.

In the present invention, the term'oligomer' may mean an aggregate of oligomer chains including the above oligomer chains.

In the present invention, 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 invention, the term'alkyl group' may mean a monovalent saturated aliphatic hydrocarbon, and may include linear alkyl groups such as methyl, ethyl, propyl, and butyl; Branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl; And a cyclic saturated hydrocarbon, or a cyclic unsaturated hydrocarbon containing one or two or more unsaturated bonds.

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

In the present invention, the term'cycloalkyl group' may mean a cyclic saturated hydrocarbon.

In the present invention, 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 invention, the term'aralkyl' is also called aralkyl and may mean a combination of an alkyl group and an aryl group formed by replacing a hydrogen atom bonded to a carbon constituting an alkyl group with an aryl group.

In the present invention, the term'single bond' may mean a single covalent bond itself that does not include a separate atom or molecular group.

In the present invention, 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.

Measurement method and conditions

In the present invention,'weight average molecular weight (Mw)','number average molecular weight (Mn)','molecular weight distribution (MWD)' and'unimodal characteristics' are measured by measuring molecular weight through GPC (Gel permeation chromatograph) analysis, and It was measured by obtaining a distribution curve. In addition, 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% by weight of an amine compound in tetrahydrofuran.

Modified conjugated diene-based copolymer

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

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a polymer chain including a repeating unit derived from a conjugated diene-based monomer; A functional group derived from a modified oligomer bonded to one end of the polymer chain; And a functional group derived from an aminoalkoxysilane modifier containing an amine group and an alkoxysilyl group bonded to the other end of the polymer chain, wherein the modified oligomer comprises a repeating unit derived from a compound containing an N-functional group and a repeating unit derived from a conjugated diene monomer. At least two oligomer chains, a unit derived from a silyl group-containing coupling agent, and a unit derived from an organometallic compound, wherein each of the oligomer chains comprises a first modified oligomer bonded to each other through the unit derived from the silyl group-containing coupling agent. It characterized in that it includes.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes an oligomer chain including a repeating unit derived from an N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer, and a unit derived from a silyl group-containing coupling agent, wherein the oligomer It is prepared by the production method described below in which at least two chains are polymerized in the presence of an oligomer-derived functional group including a first modified oligomer connected to each other by a unit derived from a silyl group-containing coupling agent. It may contain a functional group derived from a modified oligo at the terminal in a high content.

Specifically, the modified oligomer according to an embodiment of the present invention includes at least two oligomer chains including a repeating unit derived from an N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer, a unit derived from a silyl group-containing coupling agent, and an organometallic. Including a compound-derived unit, wherein each of the oligomer chains is bonded through a unit derived from the silyl group-containing coupling agent, i.e., the oligomer chains are coupled by a silyl group-containing coupling agent to intervene the unit derived from the silyl group-containing coupling agent. The modified conjugated diene-based polymer according to an embodiment of the present invention including a functional group derived from the modified oligomer at one end may include a first modified oligomer to which the oligomer chain is bonded at one end. It may have a coupling-bonded functional group derived from a one-modified oligomer, and as a result, the content of the functional group derived from a modified oligomer may be increased, so that it is highly denatured, and the filler affinity may be more excellent.

The N-functional group-containing compound may be a hydrocarbon compound containing an N-functional group in the molecule, and specifically, the N-functional group-containing compound is an amino group, amide group, imino group, imidazole group, pyri It may be an aromatic hydrocarbon compound containing an N-functional group including a midyl group or a cyclic amino group, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and It may be an alkylaryl group having 7 to 20, an arylalkyl group having 7 to 20 carbon atoms, or an alkoxysilyl group having 1 to 10 carbon atoms.

As another example, the N-functional group-containing compound may be a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A C1-C30 heteroalkyl group, a C2-C30 heteroalkenyl group; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms,

R ₄ is a single bond; An alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 5 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 ₅ is an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms; Or a functional group represented by the following Formula 1a or Formula 1b,

n is an integer of 1 to 5 _{, at least one of R 5} is a functional group represented by the following Formula 1a or Formula 1b, and when n is an integer of 2 to 5, a plurality of R ₅ may be the same or different from each other,

[Formula 1a]

In Formula 1a,

R ₆ is 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 ₇ and R ₈ are each independently an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with 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 ₉ is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; It is a C3-C30 heterocyclic group,

X is an N, O or S atom, and when X is O or S, R ₉ is absent,

[Formula 1b]

In Formula 1b,

R ₁₀ is 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 ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms, or the R ₁₁ and R ₁₂ are connected to each other to form a heterocyclic group having 2 to 20 carbon atoms together with N.

Specifically, in Formula 1, R ₁ to R ₃ are each independently hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; Or an alkynyl group having 2 to 10 carbon atoms, and R ₄ is a single bond; Or an unsubstituted C1-C10 alkylene group, R ₅ is a C1-C10 alkyl group; An alkenyl group having 2 to 10 carbon atoms; An alkynyl group having 2 to 10 carbon atoms; Or a functional group represented by the following formula 1a or formula 1b, in the formula 1a, R ₆ is an unsubstituted C 1 to C 10 alkylene group, R ₇ and R ₈ are each independently unsubstituted C 1 to 10 An alkylene group, R ₉ is an alkyl group having 1 to 10 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, in Formula 1b, R ₁₀ is an unsubstituted alkylene group having 1 to 10 carbon atoms, and R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Or an aryl group having 6 to 20 carbon atoms; It may be a heterocyclic group having 3 to 20 carbon atoms, or R ₁₁ and R ₁₂ may be connected to each other to form a heterocyclic group having 3 to 10 carbon atoms together with N.

More specifically, the compound represented by Formula 1 may be one or more selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

As another example, the oligomer chain including the repeating unit derived from the N-functional group-containing compound and the repeating unit derived from a conjugated diene-based monomer may be a molecular chain represented by Formula 3 below. In addition, as another example, an oligomer chain including a repeating unit derived from an N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer is a molecular chain in which a unit represented by the following formula (3a) and a unit represented by formula (3b) are randomly arranged. I can.

[Formula 3]

[Formula 3a]

[Formula 3b]

In Chemical Formula 3, Chemical Formula 3a, and Chemical Formula 3b, R ₄ , R ₅ and n are as defined in Chemical Formula 1, and o and p are each independently an integer of 1 to 30, specifically an integer of 1 to 20.

In addition, when the oligomer chain is a molecular chain represented by Formula 3 or a spray chain in which Formulas 3a and 3b are randomly arranged, o and p in Formulas 3, 3a and 3b are the weight of the oligomer chain in the above range. It can be appropriately adjusted so that the average molecular weight is 10,000 g/mol or less.

In addition, the silyl group-containing coupling agent may include a conventional coupling agent containing a silyl group as long as it does not adversely affect the modified conjugated diene-based polymer, and specifically, 4-(chlorodimethylsilyl)styrene (4-(chlorodimethylsilyl) )styrene).

Meanwhile, the modified oligomer according to an embodiment of the present invention polymerizes an N-functional group-containing compound and a conjugated diene-based monomer in the presence of an organometallic compound, and then performs a coupling reaction with a silyl group-containing coupling agent. It may be prepared, and accordingly, in addition to the first modified oligomer, a second modified oligomer chain including a repeating unit derived from the N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer and a unit derived from an organometallic compound It may include an oligomer, and the second modified oligomer may be one in which the coupling reaction with the silyl group-containing coupling agent is not performed after the polymerization reaction of the N-functional group-containing compound and the conjugated diene-based monomer in the presence of an organometallic compound.

That is, the modified oligomer according to an embodiment of the present invention may include a first modified oligomer or a first modified oligomer and a second modified oligomer, and the modified oligomer is a first modified oligomer and a second modified oligomer together. If included, the modified conjugated diene-based polymer according to an embodiment of the present invention may include at least two polymer chains.

Specifically, in another example of the present invention, the modified conjugated diene-based polymer includes a first polymer chain and a second polymer chain each including a repeating unit derived from a conjugated diene-based monomer, and the first polymer chain is at one end. A functional group derived from a first modified oligomer is bonded, a functional group derived from a denaturant is bonded to the other end, and a functional group derived from a second modified oligomer is bonded to one end of the second polymer chain, and a functional group derived from a modifying agent is bonded to the other end. There may be. In addition, the first polymer chain and the second polymer chain may have a weight ratio of 1:9 to 9:1.

In addition, according to an embodiment of the present invention, the modified conjugated diene-based polymer includes a monomer-derived repeating unit, a modified oligomer-derived functional group, and a denaturant-derived functional group, wherein the monomer-derived repeating unit is a conjugated diene-based monomer-derived repeating unit. It may be a unit, or it may mean a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer.

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 -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.

The aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidino ethyl) styrene (3-(2-pyrrolidino ethyl) styrene), 4-(2-pyrrolidino ethyl) styrene (4-(2-pyrrolidino) ethyl)styrene) and 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene) I can.

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 a repeating unit derived from the conjugated diene-based monomer. The diene-based monomer-derived repeating unit may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. . When the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer contains a diene-based monomer-derived repeating unit in excess of 0% to 1% by weight, more than 0% to 0.1% by weight, It may be included in an amount exceeding 0% to 0.01% by weight, or exceeding 0% 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, the main chain constituting the skeleton of the modified conjugated diene-based polymer may be a random copolymer chain, and in this case, there is an 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 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 to less than 2.0, 1.1 or more to less than 2.0, or 1.1 or more and less than 1.7, and within this range, tensile properties and viscoelasticity It has excellent properties and has an excellent balance between physical properties.

In another example, the modified conjugated diene-based polymer has a molecular weight distribution curve obtained by gel permeation chromatography (GPC) in a unimodal form, which is the molecular weight shown in the polymer polymerized by continuous polymerization. By distribution, it may mean that the modified conjugated diene-based polymer has uniform properties.

As another example, the modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared by continuous polymerization, has a unimodal molecular weight distribution curve, and a molecular weight distribution of 1.0 or more and less than 1.7.

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 to the inside of 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.

In addition, the modifier according to the present invention may be a modifier for modifying the other end of the conjugated diene-based polymer, and a specific example may be a silica affinity modifier. The silica-affinity modifier may mean a modifier containing a silica-affinity functional group in a compound used as a modifier, and the silica-affinity functional group has excellent affinity with a filler, especially a silica-based filler, It may mean a functional group capable of interaction between the functional groups derived from the denaturant.

Specifically, the modifier according to an embodiment of the present invention may be an aminoalkoxysilane modifier containing an amine group and an alkoxysilyl group, and may be a compound represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R _a1 is a single bond or an alkylene group having 1 to 10 carbon atoms,

R _a2 and R _a3 are each independently an alkyl group having 1 to 10 carbon atoms,

R _a5 may be a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms,

R _a4 is It 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, n ₁ is an integer of 1 to 3, n ₂ is an integer of 0 to 2, but when n _{2 is 0, n 1} is 1 or 2, and j is 1 It may be an integer of 30 to.

Specifically, in Formula 2, R _a1 may be a single bond or an alkylene group having 1 to 5 carbon atoms, R _a2 and R _a3 may each independently be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and R _a5 is It may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms, and R _a4 is a single bond or an alkyl group having 1 to 5 carbon atoms It may be a ene group, or -[R ⁴² O] _j -, and R ⁴² may be an alkylene group having 1 to 5 carbon atoms.

In Formula 2, when R _a5 is a heterocyclic group, the heterocyclic group may be substituted or unsubstituted with a trisubstituted alkoxysilyl group, and when the heterocyclic group is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group It may be connected to and substituted with the heterocyclic group by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxy silyl group may mean an alkoxy silyl group substituted with an alkoxy group having 1 to 10 carbon atoms. If R _{a5 is a heterocyclic group substituted with an alkoxysilyl group, n 1} and n ₂ may be adjusted so that the total number of alkoxy groups in the compound represented by Formula 1 is 6 or less.

More specifically, 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), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine), N,N-diethyl-3-(tri Ethoxysilyl)propan-1-amine (N,N-diethyl-3-(triethoxysilyl)propan-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1 ,1-trimethylsilaneamine (N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine), N,N-bis(3-(1H-imidazole-1- Yl)propyl)-(triethoxysilyl)methan-1-amine (N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine), 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), N,N-bis(2- (2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine (N,N-bis(2-(2-methoxyethoxy)ethyl) -3-(triethoxysilyl)propan-1-amine), 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), N-(2,5,8,11,14-pentaoxahexadecan-16- One)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine (N-(2,5,8,11,14-pentaoxahexadecan -16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine) and N-(3,6,9,12-tetraoxahexadecyl) -N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecane-1-amine (N-(3,6,9,12-tetraoxahexadecyl)-N-(3 -(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1-amine).

Method for producing modified conjugated diene-based copolymer

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 the steps of polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a modified oligomer to prepare an active polymer ( S1); And reacting the active polymer with an aminoalkoxysilane modifier containing an amine group and an alkoxysilyl group (S2), wherein the modified oligomer comprises a repeating unit derived from a compound containing an N-functional group and a repeating unit derived from a conjugated diene monomer. At least two oligomer chains, a unit derived from a silyl group-containing coupling agent, and a unit derived from an organometallic compound, wherein each of the oligomer chains comprises a first modified oligomer bonded to each other through the unit derived from the silyl group-containing coupling agent. It characterized in that it includes.

Conjugated diene-based monomers, aromatic vinyl-based monomers, and modified oligomers used in the preparation method are as described above.

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.

Meanwhile, the modified oligomer is prepared by reacting an N-functional group-containing compound and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of an organometallic compound to prepare an active oligomer chain, and a coupling reaction between the active oligomer chain and a silyl group-containing coupling agent. Here, the hydrocarbon solvent is as described above, and the organometallic compound is, for example, 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-heptyl Cyclohexyllithium, 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 iso It may be one or more selected from the group consisting of propylamide. In addition, the conjugated diene-based monomer used in the production of the modified oligomer may be the same as the conjugated diene-based monomer used in the production of the modified conjugated diene-based polymer.

On the other hand, the modified oligomer may provide a functional group to the polymer chain by including a unit derived from an organometallic compound and at the same time serve as a polymerization initiator, thereby performing the polymerization reaction of step (S1) without the use of a separate polymerization initiator. I can.

According to an embodiment of the present invention, the modified oligomer 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 monomer may represent the total amount of a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer.

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 comprises the step of polymerization by self-reaction heat without optionally applying heat after adding the modified oligomer. It may mean a polymerization method, and the elevated temperature polymerization may refer to a polymerization method in which heat is arbitrarily applied after adding the modified oligomer to increase the temperature, and the isothermal polymerization is performed by adding 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, and this range By narrowly controlling the molecular weight distribution of the polymer within, 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 modified oligomer.

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'-tetramethyl It may be one or more selected from the group consisting of ethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di(2-tetrahydro Furyl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and when the polar additive is included, a conjugated diene-based When a monomer and an aromatic vinyl-based monomer are copolymerized, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in reaction rate thereof.

According to an embodiment of the present invention, in the reaction of step (S2), the denaturant may 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 denaturing agent 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 denaturing oligomer in step (S1). Since the molar ratio of the denaturing agent and the modified oligomer, and the amount of the denaturing agent to the monomer, may have an effect on the glass transition temperature, Mooney viscosity, and Mooney relaxation rate of the polymer to be produced, select and apply an appropriate ratio within the above range as much as possible. It is desirable.

As another example, according to an embodiment of the present invention, the method for preparing the modified conjugated diene-based polymer may be carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and a modification reactor. As a specific example, the (S1) and (S2) steps are carried out by continuous polymerization, the (S1) step is carried out continuously in at least two polymerization reactors including the first reactor, and the first of the polymerization reactors The polymerization conversion rate in the polymerization reactor may be controlled to 50% or less. Here, the number of polymerization reactors may be flexibly determined according to reaction conditions and environments. The continuous polymerization method may refer to a reaction process in which a reactant is continuously supplied to a reactor and the produced reaction product is continuously discharged. In the case of the continuous polymerization method, there is an effect of excellent productivity and processability, and excellent uniformity of the polymer to be produced.

In addition, according to an embodiment of the present invention, when continuously preparing the active polymer in the polymerization reactor, the polymerization conversion rate in the first reactor may be 50% or less, 10% to 50%, or 20% to 50%, and , After starting the polymerization reactor within this range, it is possible to induce a polymer having a linear structure during polymerization by suppressing side reactions that occur while the polymer is formed, and the molecular weight distribution curve is unimodal and the molecular weight distribution is in the above-described range. It is possible to prepare a polymer having.

At this time, the polymerization conversion rate may be adjusted according to the reaction temperature, the residence time of the reactor, and the like.

The polymerization conversion rate may be determined by measuring the solid concentration in the polymer solution containing the polymer, for example, during polymerization of the polymer.For example, in order to secure the polymer solution, a cylindrical container is mounted at the outlet of each polymerization reactor to A positive polymer solution was filled in a cylindrical container, the cylindrical container was separated from the reactor, and the weight (A) of the cylinder filled with the polymer solution was measured, and then the polymer solution filled in the cylindrical container was added to an aluminum container, For example, transfer to an aluminum dish and measure the weight (B) of a cylindrical container from which the polymer solution has been removed, and dry the aluminum container containing the polymer solution in an oven at 140° C. for 30 minutes, and determine the weight (C) of the dried polymer. After measurement, it may be calculated according to Equation 1 below.

[Equation 1]

On the other hand, the polymerized product polymerized in the first reactor is sequentially transferred to the polymerization reactor before the transformation reactor, so that the polymerization can be carried out until the polymerization conversion rate reaches 95% or more. The polymerization conversion rate for each reactor from the second reactor or the second reactor to the polymerization reactor before the modification reactor may be appropriately adjusted for each reactor in order to control the molecular weight distribution.

Meanwhile, in the step (S1), when preparing the active polymer, the residence time of the polymer in the first reactor may be 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes, within this range, It can be easy to control the polymerization conversion rate.

In the present invention, the term'polymer' refers to (S1) step or (S2) step is completed, prior to obtaining an active polymer or a modified conjugated diene-based polymer, during step (S1), polymerization is carried out in each reactor. It may refer to an intermediate in the form of a polymer being used, and may refer to a polymer having a polymerization conversion rate of less than 90% in which polymerization is carried out in a reactor.

In addition, according to an embodiment of the present invention, the denaturant may be introduced into the denaturation reactor, and the (S2) step may be performed in the denaturation reactor. In another example, the denaturant may be added to a transport unit for transporting the active polymer prepared in step (S1) to a denaturing reactor for performing step (S2), and mixing the active polymer and the modifier in the transport unit In this case, the reaction may be performed by, and the reaction may be a modification reaction in which a modifier is simply bonded to the active polymer, or a coupling reaction in which the active polymer is connected based on the modifier.

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 reinforcing properties 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.

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

Manufacturing Example 1

In a 500 ml round bottom flask, add 100 ml of tetrahydrofuran and 1.0 g (10 wt% in n-hexane) of n-butyllithium and add 1-(4-vinylpentyl)pyrrolidine (1-(4-vinylphenethyl)pyrrolidine). ) 3.1 g (Sigma-Aldrich) and 7.6 g of 1,3-butadiene were added, followed by reaction at 10° C. for 30 minutes. Then, 0.30 g of 4-(chlorodimethylsilyl)styrene (Sigma-Aldrich) was added and a coupling reaction was performed for 10 minutes to prepare a modified oligomer having a weight average molecular weight of 5,600 g/mol.

Manufacturing Example 2

In Preparation Example 1, a modified oligomer having a weight average molecular weight of 3,500 g/mol was prepared in the same manner as in Preparation Example 1, except that 1.30 g of 4-(chlorodimethylsilyl)styrene was added.

Comparative Production Example

In a 500 ml round bottom flask, add 100 ml of tetrahydrofuran and 1.0 g (10 wt% in n-hexane) of n-butyllithium and add 1-(4-vinylpentyl)pyrrolidine (1-(4-vinylphenethyl)pyrrolidine). ) 3.1 g (Sigma-Aldrich) was added and then reacted at 10° C. for 30 minutes to prepare a denaturing initiator.

Example 1

In one of three continuous stirring liquid phase reactors (CSTR), a styrene solution in which 60% by weight of styrene is dissolved in n-hexane is dissolved at 1.92 kg/h, and 1,3-butadiene is dissolved in 60% by weight in n-hexane. The prepared 1,3-butadiene solution was 11.9 kg/h, n-hexane 47.73 kg/h, and a 1,2-butadiene solution in which 2.0 wt% of 1,2-butadiene was dissolved in n-hexane was 40 g/h, polar 53.0 g/h of a polar additive solution in which 10% by weight of 2,2-(di-2(tetrahydrofuryl)propane) was dissolved in n-hexane as an additive, and modified prepared in Preparation Example 1 in n-hexane as an initiator A modified oligomer solution in which the oligomer was dissolved in 10% by weight was injected at a rate of 1.80 kg/h. At this time, the temperature inside the reactor was maintained at 50°C, and when the polymerization conversion rate reached 45%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe ([DTP]:[act. Li]=0.6). :1.0 molar ratio).

Subsequently, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 2.95 kg/h. At this time, the temperature of the second reactor was maintained to be 65°C, and when the polymerization conversion rate became 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

Transfer the polymer from the second reactor to the third reactor, and as a denaturing agent 3-(diethoxy(methyl)silyl)-N-(3-(diethoxy(methyl)silyl)propyl)-N-methylpropane-1- A solution in which 20% by weight of amine was dissolved was added to the third reactor at a rate of 116 g/h, and the temperature of the third reactor was maintained at 65°C ([modifier]:[act. Li]=1.8: 1.0 molar ratio).

Thereafter, a solution of IR1520 (BASF) dissolved in 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 100 g/h, followed by stirring. 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 conjugated diene-based polymer at both ends. The analysis results for the modified conjugated diene-based polymer at both ends are shown in Table 1 below.

Example 2

In Example 1, the same was carried out as in Example 1, except that a modified oligomer solution in which the modified oligomer prepared in Preparation Example 2 was dissolved in 10% by weight as a modified oligomer was injected at a rate of 1.10 kg/h. , A modified styrene-butadiene copolymer was prepared ([DTP]:[act. Li]=0.6:1.0 molar ratio, [modifier]:[act. Li]=1.85:1.00 molar ratio).

Example 3

In a 20 L autoclave reactor, 3 kg of n-hexane, 95 g of the modified oligomer prepared in Preparation Example 1, 270 g of styrene, 710 g of 1,3-butadiene, and 2,2-bis(2-oxoranyl) as a polar additive The internal temperature of the reactor into which 1.29 g of propane was added was adjusted to 60°C, and adiabatic heating reaction was performed. After 30 minutes elapsed, 20 g of 1,3-butadiene was added to cap the polymer end with butadiene. After 10 minutes elapsed, 3-(diethoxy(methyl)silyl)-N-(3-(diethoxy) was added as a denaturing agent. (Methyl)silyl)propyl)-N-methylpropan-1-amine was added and reacted for 15 minutes ([DTP]:[act. Li]=0.6:1.0 molar ratio, [modifier]:[act. Li]= 1.85:1.00 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

In one of three continuous stirring liquid phase reactors (CSTR), a styrene solution in which 60% by weight of styrene is dissolved in n-hexane is dissolved at 1.92 kg/h, and 1,3-butadiene is dissolved in 60% by weight in n-hexane. The prepared 1,3-butadiene solution was 11.8 kg/h, n-hexane 47.73 kg/h, and a 1,2-butadiene solution in which 2.0 wt% of 1,2-butadiene was dissolved in n-hexane was 40 g/h, polar As an additive, a polar additive solution in which 2,2-(di-2(tetrahydrofuryl)propane) was dissolved at 10% by weight in n-hexane was 53.0 g/h, and n-butyllithium was at 10% by weight in n-hexane. The dissolved n-butyllithium solution was injected at a rate of 50.0 g/h. At this time, the temperature inside the reactor was maintained at 55°C, and when the polymerization conversion rate reached 48%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe ([DTP]:[act. Li]=0.6). :1.0 molar ratio)

Subsequently, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 2.95 kg/h. At this time, the temperature of the second reactor was maintained to be 65°C, and when the polymerization conversion rate became 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

The polymer is transferred from the second reactor to the third reactor, and a solution in which dimethyl dichlorosilane is dissolved in 20% by weight as a coupling agent is introduced into the third reactor at a rate of 33 g/h. The temperature of the reactor was maintained at 65°C ([coupling agent]:[act. Li]=1.8:1.0 molar ratio).

Thereafter, a solution of IR1520 (BASF) dissolved in 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 100 g/h, followed by stirring. 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 to prepare an unmodified conjugated diene-based polymer. The analysis results for the thus prepared unmodified styrene-butadiene copolymer are shown in Table 1 below.

Comparative Example 2

In Example 1, the above implementation except that a modified initiator solution in which the modified initiator prepared in Comparative Preparation Example was dissolved in 10% by weight was injected at a rate of 0.65 kg/h instead of the modified oligomer prepared in Preparation Example 1. In the same manner as in Example 1, a modified styrene-butadiene copolymer was prepared ([DTP]:[act. Li]=0.6:1.0 molar ratio, [modifier]:[act. Li]=1.85:1.00 molar ratio).

Comparative Example 3

In Example 1, a terminal modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the reaction with the denaturing agent was not performed ([DTP]:[act. Li]=0.6: 1.0 molar ratio).

Comparative Example 4

In Example 3, a modified styrene-butadiene copolymer was prepared in the same manner as in Example 3, except that 45 g of the modified initiator prepared in Comparative Preparation Example was used instead of the modified oligomer prepared in Preparation Example 1. ([DTP]:[act. Li]=0.6:1.0 molar ratio, [modifier]:[act. Li]=1.85:1.00 molar ratio).

Experimental Example 1

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

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

The content of styrene units (SM) and vinyl (Vinyl) in each of the polymers was 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). Samples were left at room temperature (23±3°C) for at least 30 minutes, and then 27±3 g was collected, filled in the die cavity, and platen was operated to measure for 4 minutes.

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 in a platinum 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, after storing at 0° C. for 2 hours or more, it was diluted in 30 mL of ultrapure water, and inhalation was performed to measure.

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.

division Example Comparative example One 2 3 One 2 3 4 NMR
(weight%) SM 10 10 10 10 10 10 10 Vinyl 38 38 38 38 38 38 38 GPC Mw(X10 ³ g/mol) 521 505 405 495 502 314 402 Mn(X10 ³ g/mol) 321 310 311 305 315 224 305 PDI 1.62 1.63 1.30 1.62 1.59 1.40 1.32 Mooney viscosity (MV) 55 57 49 57 59 31 48 N content (ppm) 250 301 255 - 210 139 201 Si content (ppm) 361 399 389 195 325 36 314

As shown in Table 1, in Examples 1 to 3, it was confirmed that each of the N content and the Si content contained 200 ppm or more. In relation, Comparative Example 1 did not contain N, and the Si content was also reduced to a half level compared to Examples 1 to 3. Here, Comparative Example 1 is an unmodified conjugated diene-based polymer prepared to have a molecular weight equivalent to that of the Example by using a silyl group-containing coupling agent during polymerization. It does not contain the derived functional group.

From the fact that the N and Si contents of each of Examples 1 to 3 were significantly increased compared to Comparative Example 1 as described above, Examples 1 to 3 were prepared using a modified oligomer and an aminoalkoxysilane modifier during polymerization. It can be seen that each of these derived functional groups are included in the molecule.

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions containing the modified or unmodified conjugated diene-based copolymers prepared in the above Examples and Comparative Examples and the molded articles prepared therefrom, tensile properties and viscoelastic properties were measured, respectively, and the results were obtained. It is shown in Table 3 below.

1) Preparation of rubber specimen

The modified or unmodified conjugated diene polymers of Examples, Comparative Examples and Reference Examples were used as raw rubbers and were blended under the 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.

division Raw material Content (parts by weight) 1st stage kneading Rubber 100 Silica 70 Coupling agent (X50S) 11.2 Fair oil 37.5 Zinc agent 3 Stearic acid 2 Antioxidant 2 Anti-aging agent 2 Wax One 2nd stage kneading sulfur 1.5 Rubber accelerator 1.75 Vulcanization accelerator 2

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

2) Tensile characteristics

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

3) Viscoelastic properties

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

4) Processability characteristics

1) The Mooney viscosity (MV, (ML1+4, @100°C) MU) of the 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, but in Table 3 below, it is expressed in Index (%) based on the result value of Comparative Example 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.

division Example Comparative example One 2 3 One 2 3 4 Tensile properties Tensile strength (kgf/cm ² ) 166 168 163 153 161 145 162 300% modulus (kgf/cm ² ) 114 116 114 92 111 89 113 Viscoelastic properties tan δ(at 0℃, Index) 103 104 101 100 102 95 99 tan δ(at 60℃, Index) 126 129 125 100 119 102 121 Processability characteristics (Index) 103 104 107 100 92 110 89

As shown in Table 3, Examples 1 to 3 exhibited improved tensile properties compared to Comparative Examples 1 to 4 while at the same time exhibiting remarkably improved effects in viscoelastic properties and processability properties.

Specifically, Examples 1 and 2 exhibited equal or higher tensile properties and wet road surface resistance (0°C tan δ value) than Comparative Example 2, while rolling resistance characteristics (fuel efficiency, 60°C tan δ value) were about 105% and 108, respectively. %, and at the same time, the processability properties were also greatly improved to about 112%, respectively. In addition, Examples 1 and 2 showed remarkably improved effects in tensile properties and viscoelastic properties compared to Comparative Example 3. At this time, Comparative Example 2 was prepared in the same manner as in Example 1, except that the modified initiator prepared in Comparative Preparation Example was used instead of the modified oligomer presented in the present invention as an initiator, and Comparative Example 3 was presented in the present invention. It was prepared in the same manner as in Example 1, except that a denaturant was not applied.

In addition, Example 3 exhibited the same level of tensile properties and wet road resistance as compared to Comparative Example 4, while the rolling resistance property was increased by about 3%, and at the same time, the workability property was increased to about 20%, showing a remarkable improvement effect in the processability property. In this case, Comparative Example 4 was prepared in the same manner as in Example 3, except that the modified initiator prepared in Comparative Preparation Example was used instead of the modified oligomer presented in the present invention as an initiator.

The above results show that the modified conjugated diene-based polymer of the present invention is prepared by applying a modified oligomer as an initiator and an aminoalkoxysilane-based modifying agent as a modifying agent, thereby including the modified oligomer and functional groups derived from the modifying agent in the polymer chain. It means that both viscoelastic properties and processability have excellent effects in a good balance.

Claims (18)

A polymer chain containing a repeating unit derived from a conjugated diene-based monomer;
A functional group derived from a modified oligomer bonded to one end of the polymer chain; And
And a functional group derived from an aminoalkoxysilane modifier containing an amine group and an alkoxysilyl group bonded to the other end of the polymer chain,
The modified oligomer includes at least two oligomer chains including a repeating unit derived from an N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer, a unit derived from a silyl group-containing coupling agent, and a unit derived from an organometallic compound, each of the oligomer chains Is a modified conjugated diene-based polymer comprising a first modified oligomer bonded via a unit derived from the silyl group-containing coupling agent therebetween.
The method of claim 1,
The modified oligomer is a modified conjugated diene-based polymer further comprising an oligomer chain including a repeating unit derived from an N-functional group-containing compound and a conjugated diene-based monomer, and a second modified oligomer including a unit derived from an organometallic compound.
The method of claim 2,
Each includes a first polymer chain and a second polymer chain including repeating units derived from conjugated diene-based monomers,
In the first polymer chain, a functional group derived from a first modified oligomer is bonded to one end, and a functional group derived from a modifying agent is bonded to the other end,
The second polymer chain is a modified conjugated diene-based polymer in which a functional group derived from a second modified oligomer is bonded to one end and a functional group derived from a modifying agent is bonded to the other end.
The method of claim 1,
A modified conjugated diene polymer having a molecular weight distribution curve obtained by gel chromatography having a unimodal shape and a molecular weight distribution of 1.0 or more and less than 2.0.
The method of claim 1,
The N-functional group-containing compound is an aromatic hydrocarbon compound containing an N-functional group including an amino group, an amide group, an imino group, an imidazole group, a pyrimidyl group or a cyclic amino group substituted or unsubstituted with a substituent, wherein the substituent Is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or an alkoxysilyl group having 1 to 10 carbon atoms Phosphorus-modified conjugated diene-based polymer.
The method of claim 1,
The N-functional group-containing compound is a modified conjugated diene-based polymer that is a compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ to R ₃ are each independently hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A C1-C30 heteroalkyl group, a C2-C30 heteroalkenyl group; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms,
R ₄ is a single bond; An alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent; A cycloalkylene group having 5 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 5 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 ₅ is an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms; Or a functional group represented by the following Formula 1a or Formula 1b,
n is an integer of 1 to 5 _{, at least one of R 5} is a functional group represented by the following Formula 1a or Formula 1b, and when n is an integer of 2 to 5, a plurality of R ₅ may be the same or different from each other,
[Formula 1a]

In Formula 1a,
R ₆ is 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 ₇ and R ₈ are each independently an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with 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 ₉ is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; It is a C3-C30 heterocyclic group,
X is an N, O or S atom, and when X is O or S, R ₉ is absent,
[Formula 1b]

In Formula 1b,
R ₁₀ is 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 ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Or a C 3 to C 30 heterocyclic group, wherein R ₁₁ and R ₁₂ are connected to each other to form a C 2 to C 20 heterocyclic group together with N.
The method of claim 6,
In Formula 1, R ₁ to R ₃ are each independently hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; Or an alkynyl group having 2 to 10 carbon atoms,
R ₄ is a single bond; Or an unsubstituted C1 to C10 alkylene group,
R ₅ is an alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; An alkynyl group having 2 to 10 carbon atoms; Or a functional group represented by the following Formula 1a or Formula 1b,
In Formula 1a, R ₆ is an unsubstituted alkylene group having 1 to 10 carbon atoms, R ₇ and R ₈ are each independently an unsubstituted alkylene group having 1 to 10 carbon atoms _{, and R 9 is an alkyl group having 1 to 10 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,
In Formula 1b,
R ₁₀ is an unsubstituted C 1 to C 10 alkylene group,
R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Or a C 3 to C 20 heterocyclic group, wherein R ₁₁ and R ₁₂ are connected to each other to form a C 2 to C 10 heterocyclic group with N is a modified conjugated diene-based polymer.
The method of claim 1,
The N-functional group-containing compound is one or more selected from the group consisting of compounds represented by the following formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.
The method of claim 1,
The coupling agent is a modified conjugated diene-based polymer that is 4-(chlorodimethylsilyl)styrene.
The method of claim 1,
The modified conjugated diene polymer is a compound represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
R _a1 is a single bond or an alkylene group having 1 to 10 carbon atoms,
R _a2 and R _a3 are each independently an alkyl group having 1 to 10 carbon atoms,
R _a5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms,
R _a4 is A single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, and R ⁴² is an alkylene group having 1 to 10 carbon atoms,
n ₁ is an integer of 1 to 3, n ₂ is an integer of 0 to 2, but when n _{2 is 0, n 1} is 1 or 2, and j is an integer of 1 to 30.
The method of claim 10,
In Formula 2, R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 5 carbon atoms,
R _a2 and R _a3 are each independently an alkyl group having 1 to 5 carbon atoms,
R _a5 is a modified conjugated diene-based polymer which is a hydrogen atom, a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
Preparing an active polymer by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a modified oligomer (S1); And
And reacting the active polymer with an aminoalkoxysilane modifier containing an amine group and an alkoxysilyl group (S2),
The modified oligomer includes at least two oligomer chains including a repeating unit derived from an N-functional group-containing compound and a repeating unit derived from a conjugated diene-based monomer, a unit derived from a silyl group-containing coupling agent, and a unit derived from an organometallic compound, each of the oligomer chains The method for producing a modified conjugated diene-based polymer according to claim 1, comprising a first modified oligomer bonded through a unit derived from the silyl group-containing coupling agent therebetween.
The method of claim 12,
The modified oligomer is prepared by reacting an N-functional group-containing compound and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of an organometallic compound to prepare an active oligomer chain, and a coupling reaction between the active oligomer chain and a coupling agent. Method for producing a diene-based polymer.
The method of claim 12,
The modified oligomer further comprises a second modified oligomer including an oligomer chain including a repeating unit derived from an N-functional group-containing compound and a conjugated diene-based monomer and a unit derived from an organometallic compound. Manufacturing method.
The method of claim 12,
The method for producing a modified conjugated diene-based polymer wherein the N-functional group-containing compound is at least one selected from the group consisting of compounds represented by the following formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.
The method of claim 12,
The modified oligomer is a method for producing a modified conjugated diene-based polymer to be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers.
The method of claim 12,
The (S1) and (S2) steps are carried out by continuous polymerization,
The (S1) step is carried out in at least two polymerization reactors, and the polymerization conversion rate in the first polymerization reactor of the polymerization reactor is controlled to 50% or less.
100 parts by weight of the modified conjugated diene-based polymer of claim 1; And
The rubber composition containing 0.1 parts by weight to 200 parts by weight of a filler.