KR20200019105A - Modified conjugated diene polymer and preparation method thereof - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer comprising a functional group derived from a modified polymerization initiator capable of providing a filler affinity functional group to a polymer chain, a preparation method thereof, and a rubber composition comprising the modified conjugated diene-based polymer. According to the present invention, the modified conjugated diene-based polymer exhibits excellent processability, mechanical properties and viscoelasticity.

Description

Modified conjugated diene polymer and preparation method thereof

The present invention relates to a modified conjugated diene-based polymer including a functional group derived from a modified polymerization initiator and excellent in affinity with a filler, and having improved mechanical and viscoelastic properties, and a method of preparing the same.

In recent years, with the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers having low running resistance, excellent abrasion resistance and tensile properties, and a control stability typified by wet skid resistance.

In order to reduce the running 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, a rebound elasticity of 50 ° C. to 80 ° C., tan δ, Goodrich heat generation and the like are used. That is, a rubber material having a high resilience at the above temperature, or a small tan δ or good rich 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 wet skid resistance. Recently, conjugated diene-based (co) polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and 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 controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final produced SBR or BR rubber, and the movement of the chain ends by the binding or modification of the chain ends can be reduced and the bonding strength with fillers such as silica or carbon black can be increased. It is widely used as a rubber material for tires.

When the solution-polymerized SBR is used as a rubber material for tires, the vinyl content in the SBR is increased to increase the glass transition temperature of the rubber, thereby controlling tire required properties such as running resistance and braking force, and properly adjusting the glass transition temperature. By adjusting the fuel consumption can be reduced.

Therefore, as a method for improving the dispersibility of fillers such as SBR and silica or carbon black, a method of modifying the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organolithium into a functional group capable of interacting with the filler has been proposed. . For example, a method of modifying the polymerizable active end of the conjugated diene polymer with a tin compound, introducing an amine group, or modifying with an alkoxysilane derivative has been proposed.

For example, US Pat. No. 4,397,994 discloses a technique in which an active anion at a polymer chain end obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, a monofunctional initiator, is bound using a binder such as a tin compound. .

On the other hand, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as reinforcing fillers, low hysteresis loss and wet skid resistance are improved. However, the hydrophilic surface silica has a disadvantage of poor dispersibility due to low affinity with rubber compared to the hydrophobic surface carbon black, so that a separate silane coupler is used to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a ring agent.

Thus, a method of introducing a functional group having affinity or reactivity with silica to the rubber molecule terminal has been made, but the effect is insufficient.

Therefore, there is a need for development of a rubber having high affinity with fillers including silica.

US 4,397,994 A

The present invention has been made to solve the problems of the prior art, to provide a modified conjugated diene-based polymer having improved affinity and mechanical properties and viscoelastic properties, including a modified polymerization initiator-derived functional group The purpose.

Another object of the present invention is to provide a method for producing the modified conjugated diene polymer.

In addition, an object of the present invention is to provide a rubber composition comprising the modified conjugated diene-based polymer and a filler.

In order to solve the above problems, the present invention includes a modified polymerization initiator-derived functional group at at least one terminal, the modified polymerization initiator is a modified conjugated diene which is a reaction product of the compound represented by the formula The system polymer is provided:

[Formula 1]

In Chemical Formula 1,

R ₁ is hydrogen, an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with substituent X, a cycloalkyl group having 1 to 20 carbon atoms substituted or unsubstituted with substituent X or an aryl having 6 to 30 carbon atoms unsubstituted or substituted with substituent X Gigi,

R ₂ is an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with substituent X,

R ₃ is hydrogen,

X is a substituent selected from the group consisting of a hydroxyl group (OH), a halogen group, a primary amino group (NH ₂ ) and a secondary amino group,

At least one of R ₁ and R ₂ is necessarily substituted with a substituent X.

In addition, the present invention is derived from a compound represented by the following formula (1) at least at one end by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of a modified polymerization initiator represented by the formula (1) in a hydrocarbon solvent Provided is a method of preparing a modified conjugated diene polymer comprising the step of preparing an active polymer having a functional group bonded thereto:

[Formula 1]

In Chemical Formula 1,

R ₁ is hydrogen, an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with substituent X, a cycloalkyl group having 1 to 20 carbon atoms substituted or unsubstituted with substituent X or an aryl having 6 to 30 carbon atoms unsubstituted or substituted with substituent X Gigi,

R ₂ is an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with substituent X,

R ₃ is hydrogen,

X is a substituent selected from the group consisting of a hydroxyl group (-OH), a halogen group, a primary amino group (-NH ₂ ) and a secondary amino group (-NHR '), and when X is a secondary amino group, R' is An alkyl group having 1 to 10 carbon atoms,

At least one of R ₁ and R ₂ is necessarily substituted with a substituent X.

The modified conjugated diene-based polymer according to the present invention may be excellent in affinity with a filler such as a silica-based filler by including a modified polymerization initiator-derived functional group at one end, it may be excellent in workability, mechanical properties and viscoelasticity have.

In addition, the production method according to the present invention can easily introduce a functional group derived from a specific modified polymerization initiator in the present invention at one end of the polymer chain by preparing the active polymer in the presence of a modified polymerization initiator of a specific structure, so that a functional group is introduced at at least one end. The modified high-modified conjugated diene-based polymer can be easily produced.

 In addition, the rubber composition comprising the modified conjugated diene-based polymer according to the present invention may be excellent in workability by including a modified conjugated diene-based polymer having excellent affinity with the filler, and as a result prepared by using the rubber composition Workpieces can be excellent in tensile strength, wear resistance and wet road resistance properties.

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

The terms or words used in this specification and claims should not be construed as being limited to the common or dictionary meanings, and the inventors can appropriately define the concept of terms in order to best explain their invention in the best way possible. It should be interpreted as meanings and concepts corresponding to the technical idea of the present invention based on the principle that the present invention.

As used herein, the term "substituted" may mean that the hydrogen of the functional group, atomic group or compound is substituted with a specific substituent, and is present in the functional group, atomic group or compound when hydrogen of the functional group, atomic group or compound is substituted with a specific substituent. One or two or more substituents may be present depending on the number of hydrogen. In addition, when a plurality of substituents are present, each of the substituents may be the same or different from each other.

As used herein, the term "alkyl group" may mean a monovalent aliphatic saturated hydrocarbon, and may be linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl and sec-butyl. And branched alkyl groups such as tert-butyl and neo-pentyl may be included.

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 invention, "cycloalkyl group" may mean a cyclic saturated hydrocarbon.

As used herein, the term “aryl group” may mean a cyclic aromatic hydrocarbon, and may also include 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 hydrocarbons) may include both.

As used herein, the terms "derived unit" and "derived functional group" may refer to a component, structure, or the substance itself resulting from a substance.

The present invention provides a modified conjugated diene-based polymer having at least one functional group derived from a modified polymerization initiator and having excellent affinity with a filler, particularly a silica-based filler.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a functional group derived from a modified polymerization initiator at at least one terminal, wherein the modified polymerization initiator is a reaction product of a compound represented by the following formula (1) with an organometallic compound It features.

 [Formula 1]

In Chemical Formula 1,

R ₁ is hydrogen, an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with substituent X, a cycloalkyl group having 1 to 20 carbon atoms substituted or unsubstituted with substituent X or an aryl having 6 to 30 carbon atoms unsubstituted or substituted with substituent X Can be

R ₂ may be an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with substituent X,

R ₃ may be hydrogen,

X may be a substituent selected from the group consisting of a hydroxyl group (-OH), a halogen group, a primary amino group (-NH ₂ ) and a secondary amino group (-NHR '), when X is a secondary amino group 'May be an alkyl group having 1 to 10 carbon atoms,

At least one of R ₁ and R ₂ is necessarily substituted with a substituent X.

Specifically, in Formula 1, R ₁ may be hydrogen, an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with substituent X or an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with substituent X, and R ₂ is a substituent It may be an alkylene group having 1 to 3 carbon atoms unsubstituted or substituted with X, substituent X is from the group consisting of a hydroxyl group (OH), a halogen group, a primary amino group (NH ₂ ) and a secondary amino group as described above It may be one or more substituents selected, at least one of R ₁ and R ₂ may be necessarily a substituent X. More specifically, the substituent X may be one or more substituents selected from the group consisting of a hydroxyl group, a halogen group and a primary amino group.

Further, in the present invention, the secondary amino group may be a substituent represented by -NHR ', wherein R' may be an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, for example, R ' May be a methyl group or an ethyl group.

In addition, in the present invention, the halogen group of the substituent X may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), specifically fluorine (F) or chlorine (Cl) Can be.

More specifically, in one embodiment of the present invention, the compound represented by Chemical Formula 1 may include one or more selected from the compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

R ₄ may be an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

R ₅ to R ₁₁ may be each independently hydrogen, a substituent X, or an alkyl group having 1 to 10 carbon atoms,

In Formula 2, at least one of R ₅ to R ₇ may be a substituent X, in Formula 3, at least one of R ₅ to R ₉ may be a substituent X, and in Formula 4, at least one of R ₅ to R ₁₁ . This substituent may be X.

In addition, R ₃ and X are as defined in the formula (1).

More specifically, the modified polymerization initiator represented by Chemical Formula 1 in one embodiment of the present invention is to include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 2a, 2b, 3a, 3b, 4a and 4b Can be.

[Formula 2a]

[Formula 2b]

[Formula 3a]

[Formula 3b]

 [Formula 4a]

[Formula 4b]

In the formula 2a, 2b, 3a, 3b, 4a and 4b,

R ₄ may be an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 20 carbon atoms,

R _5, R _6, R ₈ and R ₉ may be each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

R ₃ and X are as defined in formula (1).

More specifically, the compound represented by Chemical Formula 1 may include one or more of the compounds represented by the following Chemical Formulas 1-1 to 1-15.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

The modification initiator according to an embodiment of the present invention is produced by reacting a compound represented by Formula 1 with an organometallic compound, and may initiate a polymerization and introduce a functional group at one end of a polymer chain formed by polymerization at the same time. It may be.

In addition, the organometallic compound may be an organoalkali metal compound, and for example, may be one or more selected from an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.

Specifically, the organometallic compound is methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1-naphthyl It may be one or more selected from lithium, n-ecolithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium.

In addition, the reaction product produced by the reaction of the compound represented by Formula 1 with the organometallic compound, for example, in Formula 1, the substituent X is a hydroxyl group (-OH), a primary amino group (-NH ₂ ) or a secondary amino group When (-NHR ') is, hydrogen present in the substituent and hydrogen at the position of R ₃ may be substituted with an organometallic. Herein, the hydrogen-substituted organometallic group present in the substituent X may serve as a protecting group to protect the oxygen atom of the hydroxyl group, the nitrogen atom of the primary or secondary amino group, and the polymerization reaction may be performed by R _3. May be initiated from carbon. As an example, even if both of R ₃ and the hydrogen of the substituent X is substituted with an organometallic, only carbon to which R ₃ is bonded may form a polymerization initiation point.

In addition, in the process of stopping the polymerization by adding ethanol or the like after the polymerization reaction in the present invention, since the organometallic bonded to the substituent X is again substituted with hydrogen, the compound represented by the formula (1) in the conjugated diene-based polymer Derived functional groups may be included.

The modified conjugated diene-based polymer according to the present invention may be prepared by the production method described below, for example, may be a modified polymer of a homopolymer of conjugated diene monomer or a copolymer of conjugated diene monomer and an aromatic vinyl monomer. have. In this case, the copolymer may be a random copolymer.

Here, the "random copolymer" may indicate that the modified structural units constituting the copolymer are randomly arranged.

The modified conjugated diene-based polymer according to an embodiment of the present invention may be prepared in the presence of the modified polymerization initiator to include at least one terminal-derived functional group derived from the modified polymerization initiator. In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a functional group derived from the modified polymerization initiator at one end of the polymer chain, a functional group derived from a modifier at the other end. That is, in this case, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a sock end modified conjugated diene-based polymer in which both ends are modified.

End-modified conjugated diene-based polymers, unlike in-chain modified conjugated diene-based polymers, can bind fillers to the ends of the polymer, thus reducing the number of end-exposed polymer chains when formulating rubber compositions. have. As the number of polymer chains exposed at the end increases, the heat loss and energy loss due to friction increase in the rubber composition formulation, and thus reducing the heat loss and energy loss when reducing the number of polymer chains exposed at the ends further improves fuel economy. You can.

Here, the denaturant may be a compound that can impart a functional group to the polymer or increase the molecular weight by coupling, such as an alkoxy silane group, azacyclopropane group, ketone group, carboxyl group, thiocarboxyl group, carbonate, carboxylic acid Anhydrides, carboxylic acid metal salts, acid halides, urea groups, thiourea groups, amide groups, thioamide groups, isocyanate groups, thioisocyanate groups, halogenated isocyano groups, epoxy groups, thioethoxy groups, imine groups, and YZ bonds (here, Wherein Y is Sn, Si, Ge, or P, and Z is a halogen group), and the denaturing agent may be a compound including the functional group and not containing an onium salt. Can be.

That is, the modified conjugated diene-based polymer has a hydroxyl group (-OH), a halogen group (-X'.X ': halogen atom), a primary amino group (- NH ₂ ) or a secondary amino group and two sulfur containing groups. Here, the sulfur-containing group has an effect of further improving affinity with the filler due to the chelating property of the sulfur atom, and the hydroxyl group, the halogen group, the primary and the secondary amino group are combined with the filler (for example, silica). By hydrogen bonding, the affinity with the functional group on the filler surface can be improved further.

 Therefore, the modified conjugated diene-based polymer according to an embodiment of the present invention may be excellent in affinity with a filler, in particular a silica-based filler by including a functional group-derived functional group represented by the formula (1) at one end, The blending properties with the filler may be excellent, so that the processability of the rubber composition including the modified conjugated diene-based polymer may be improved, and as a result, the tensile strength, wear resistance, and viscoelasticity of a molded article, such as a tire, manufactured using the rubber composition. Properties can be improved.

In addition, the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 100,000 g / mol to 800,000 g / mol, specifically 200,000 g / mo to 500,000 g / mol.

In addition, the modified conjugated diene-based polymer may have a weight average molecular weight (Mw) of 200,000 g / mol to 2,500,000 g / mol, specifically 300,000 g / mol to 1,200,000 g / mol.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn; polydispersity) of 1.0 to 3.0. Specifically, the molecular weight distribution may be 1.0 to 2.5.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention has a weight distribution range as described above when considering the good effect of balancing the mechanical properties, elastic modulus and processability of the rubber composition when applied to the rubber composition The average molecular weight and the number average molecular weight may be one that satisfies the conditions of the above-mentioned range at the same time.

Specifically, the modified conjugated diene-based polymer may have a molecular weight distribution of 3.0 or less, a weight average molecular weight of 200,000 g / mol to 2,500,000 g / mol, a number average molecular weight of 100,000 g / mol to 800,000 g / mol More specifically, the molecular weight distribution may be 2.5 or less, a weight average molecular weight of 300,000 g / mol to 1,200,000 g / mol, and a number average molecular weight of 200,000 g / mol to 500,000 g / mol.

Here, the weight average molecular weight and the number average molecular weight are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), respectively, and the molecular weight distribution (Mw / Mn) is also called polydispersity, and the weight average molecular weight (Mw). ) And the number average molecular weight (Mn) (Mw / Mn).

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, more specifically 10% by weight to 50% by weight, and the glass transition temperature when the vinyl content is in the above range. Can be adjusted to an appropriate range, and when applied to a tire, not only the properties required for the tire such as driving resistance and braking force are excellent, but also it has an effect of reducing fuel consumption.

In this case, the vinyl content represents the content of 1,2-added conjugated diene monomer, not 1,4-addition, based on 100% by weight of the conjugated diene polymer composed of a monomer having a vinyl group or a conjugated diene monomer.

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

According to one embodiment of the present invention, in the hydrocarbon solvent, the modified initiator-based functional group is polymerized at least at one end by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in the presence of a modified polymerization initiator. Including the step (step 1) of preparing the active polymer, wherein the modified polymerization initiator is characterized in that the reaction product prepared by reacting the compound represented by the formula (1) and the organometallic compound.

 [Formula 1]

In Chemical Formula 1,

R ₁ is hydrogen, an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with substituent X, a cycloalkyl group having 1 to 20 carbon atoms substituted or unsubstituted with substituent X or an aryl having 6 to 30 carbon atoms unsubstituted or substituted with substituent X Can be

R ₂ may be an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with substituent X,

R ₃ may be hydrogen,

X may be a substituent selected from the group consisting of a hydroxyl group (-OH), a halogen group, a primary amino group (-NH ₂ ) and a secondary amino group (-NHR '), when X is a secondary amino group 'May be an alkyl group having 1 to 10 carbon atoms,

At least one of R ₁ and R ₂ is necessarily substituted with a substituent X.

In addition, the compound represented by the formula (1) applied to the method for producing a modified conjugated diene polymer of the present invention is as defined in the modified conjugated diene polymer. For example, the compound represented by Chemical Formula 1 may specifically include one or more of the compounds represented by Chemical Formulas 2 to 4, 2a, 2b, 3a, 3b, 4a, and 4b, and more specifically, Chemical Formula 1-1 It may include one or more of the compounds represented by 1-15.

Step 1 is a step for preparing an active polymer derived from a modified polymerization initiator at least one end, that is, a functional group derived from the reaction product of the compound represented by the formula (1) and the organometallic compound, the presence of the modified polymerization initiator in a hydrocarbon solvent It can be carried out by polymerizing the lower conjugated diene monomer or aromatic vinyl monomer and conjugated diene monomer.

The conjugated diene monomer is not particularly limited, but for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.

When the conjugated diene monomer and the aromatic vinyl monomer are used together as the monomer, the conjugated diene monomer may include 60% by weight or more of the unit derived from the conjugated diene monomer in the finally prepared modified conjugated diene polymer. It may be used in an amount of 60 wt% or more but less than 100 wt%, more specifically, 60 wt% to 85 wt%.

The aromatic vinyl monomer is not particularly limited, but for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p It may be one or more selected from the group consisting of -methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.

When the conjugated diene monomer and the aromatic vinyl monomer are used together as the monomer, the aromatic vinyl monomer may be 40% by weight or less of the aromatic vinyl monomer-derived unit in the finally prepared modified conjugated diene polymer. 40 wt% or more, more than 0 wt%, more specifically, may be used in an amount comprised from 15 wt% to 40 wt%.

The hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

The modified polymerization initiator may be used in 0.05 to 1 part by weight based on 100 parts by weight of the total monomer, specifically, may be used in 0.05 to 0.3 parts by weight.

The polymerization may be carried out by further adding a polar additive as needed, the polar additive may be added to 0.001 parts by weight to 10 parts by weight based on 100 parts by weight of the total monomer. Specifically, the content may be added in an amount of 0.001 part by weight to 1 part by weight, more specifically 0.005 part by weight to 0.2 part by weight, based on 100 parts by weight of the total monomers.

The polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis It may be one or more selected from the group consisting of (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.

In the manufacturing method according to an embodiment of the present invention, when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive, the reaction rate can be easily compensated for by forming a random copolymer. Can be induced.

In addition, the polymerization may be elevated temperature polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization).

Herein, the constant temperature polymerization refers to a polymerization method including the step of polymerizing with self-heating reaction without adding heat after the polymerization is initiated, and the elevated temperature polymerization is a polymerization method in which the temperature is increased by optionally applying heat after the polymerization is started. The isothermal polymerization refers to a polymerization method in which heat is increased after the initiation of the polymerization to increase heat or take away heat to keep the temperature of the polymer constant.

The polymerization may be performed at a temperature range of -20 ° C to 200 ° C, specifically 20 ° C to 150 ° C, more specifically, to be performed for 15 minutes to 3 hours at a temperature range of 30 ° C to 120 ° C. Can be. If carried out in the above temperature range, it is easy to control the polymerization reaction, it may be excellent in the polymerization rate and efficiency.

In addition, the method for preparing the modified conjugated diene-based polymer according to an embodiment of the present invention may further comprise the step (step 2) of reacting the active polymer prepared in step 1 with a modifier.

The reaction of step 2 is a modification reaction for introducing a functional group into the active polymer after polymerization, the reaction may be performed for 10 minutes to 5 hours at a temperature range of 10 ℃ to 120 ℃.

Here, the denaturant may be a compound that can impart a functional group to the polymer or increase the molecular weight by coupling, such as an alkoxy silane group, azacyclopropane group, ketone group, carboxyl group, thiocarboxyl group, carbonate, carboxylic acid Anhydrides, carboxylic acid metal salts, acid halides, urea groups, thiourea groups, amide groups, thioamide groups, isocyanate groups, thioisocyanate groups, halogenated isocyano groups, epoxy groups, thioethoxy groups, imine groups, and YZ bonds (here, Wherein Y is Sn, Si, Ge, or P, and Z is a halogen group), and the denaturing agent may be a compound including the functional group and not containing an onium salt. Can be.

In addition, the denaturing agent may be used in 0.1 mol to 5.0 molar ratio of 1 mole of the modified polymerization initiator. When the denaturant is used in an amount within the above ratio range, it is possible to perform a modification reaction of optimum performance, thereby obtaining a conjugated diene polymer having a high modification rate.

In addition, the modified conjugated diene-based polymer manufacturing method according to an embodiment of the present invention may be carried out by a batch polymerization (batch) or a continuous polymerization method comprising one or more reactors.

In addition, the method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by using the isopropanol solution of ethanol, 2,6-di-t-butyl-p-cresol (BHT) after preparing the active polymer It can be added to the polymerization reaction system to stop the polymerization reaction. Thereafter, a modified conjugated diene-based polymer may be obtained through desolvent treatment or vacuum drying such as steam stripping to lower the partial pressure of the solvent through supply of steam. In addition, the reaction product obtained as a result of the above-mentioned modification reaction may include an active polymer which is not modified, together with the above-mentioned modified conjugated diene polymer.

The production method according to an embodiment of the present invention may further include at least one step of recovering and drying the solvent and the unreacted monomer, if necessary, after the polymerization of Step 1, and the post-process step may include, for example, the reaction product. Put into hot water heated with steam and stirred to remove the solvent, roll drying to remove the residual amount of solvent and water may be performed.

In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a molded article prepared from the rubber composition.

The rubber composition according to an embodiment of the present invention is 0.1 to 100% by weight of the modified conjugated diene-based polymer, specifically 10 to 100% by weight, more specifically 20 to 90% by weight It may be to include. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, improvement effects such as abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, the modified conjugated diene copolymer may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight.

The rubber component may be natural rubber or synthetic rubber, for example, the rubber component may 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 obtained by modifying or refining 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, butyl rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more thereof may be used. have.

In addition, the rubber composition may include 0.1 parts by weight to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer, and the filler may include silica, carbon black, or a combination thereof. For example, the filler may include a silica-based filler.

Although the carbon black filler is not particularly limited, for example, the nitrogen adsorption specific surface area (N 2 SA, measured in accordance with JIS K 6217-2: 2001) may be 20 m 2 / g to 250 m 2 / g. In addition, the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc / 100g to 200 cc / 100g. When the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² / g, the workability of the rubber composition may be lowered. When the carbon adsorption specific surface area is less than 20 m ² / g, the reinforcement performance by the carbon black may be insignificant. In addition, when the DBP oil absorption of the carbon black exceeds 200 cc / 100 g, the workability of the rubber composition may be lowered. If the DBP oil absorption of the carbon black is less than 80 cc / 100 g, the reinforcing performance by the carbon black may be insignificant.

In addition, the silica is not particularly limited, but may be, for example, wet silica (silicate silicate), dry silica (silicate anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be a wet silica having the most remarkable effect of improving the fracture characteristics and a wet grip. In addition, the silica has a nitrogen adsorption specific surface area (N2SA) of 120 m 2 / g to 180 m 2 / g, and CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 m 2 / g to 200 m 2 / g Can be. When the nitrogen adsorption specific surface area of the said silica is less than 120 m <2> / g, there exists a possibility that the reinforcement performance by a silica may fall, and when it exceeds 180 m <2> / g, there exists a possibility that the workability of a rubber composition may fall. In addition, when the CTAB adsorption specific surface area of the silica is less than 100 m 2 / g, reinforcing performance by silica as a filler may be deteriorated, and when it exceeds 200 m 2 / g, the workability of the rubber composition may be deteriorated.

Meanwhile, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasul Feed, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

In addition, in the rubber composition according to one embodiment of the present invention, since the modified conjugated diene-based polymer in which a functional group having high affinity with a filler is introduced into the active site is used as the rubber component, the compounding amount of the silane coupling agent is It can be reduced than usual. Specifically, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the filler. When used in the above-mentioned range, the gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, the silane coupling agent may be used in 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus 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. When included in the content range, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.

In addition, the rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, when included in the content, it is possible to prevent the degradation of tensile strength, low heat generation (low fuel efficiency) of the vulcanized rubber.

In addition, as the anti-aging agent, specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.

The molded article manufactured using the rubber composition may include a tire or a tire tread.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

Preparation Example 1

360 ml of normal hexane, 95 g of a compound represented by the following formula (i) and 180 ml of n-butyllithium, 2,5 M in normal hexane were added to a 1 L autoclave reactor, and reacted at 0 ° C. for 30 minutes to prepare a modified polymerization initiator. It was. 1,10-phenanthroline titration method (D. E. Bergbreiter, E. Pendergrass, J. Org. Chem. 1981, 46, 219-220) confirmed that the concentration of denaturation initiator solution is 0.35 M.

Preparation Example 2

Preparation Example As starting material, a modification initiator solution was prepared in the same manner as in Preparation Example 1, except that Chemical Formula (ii) was used. 1,10-phenanthroline titration method (D. E. Bergbreiter, E. Pendergrass, J. Org. Chem. 1981, 46, 219-220) confirmed that the concentration of denaturation initiator solution is 0.35 M.

Preparation Example 3

Preparation Example As a starting material, a modification initiator solution was prepared in the same manner as in Preparation Example 1, except that Chemical Formula (iii) was used. 1,10-phenanthroline titration method (D. E. Bergbreiter, E. Pendergrass, J. Org. Chem. 1981, 46, 219-220) confirmed that the concentration of denaturation initiator solution is 0.35 M.

Preparation Example 4

Preparation Example As starting material A denaturation initiator solution was prepared in the same manner as in Preparation Example 1, except that Chemical Formula (iv) was used. 1,10-phenanthroline titration method (D. E. Bergbreiter, E. Pendergrass, J. Org. Chem. 1981, 46, 219-220) confirmed that the concentration of denaturation initiator solution is 0.35 M.

Preparation Example 5

Preparation Example As a starting material, a modification initiator solution was prepared in the same manner as in Preparation Example 1, except that Chemical Formula (v) was used. 1,10-phenanthroline titration method (D. E. Bergbreiter, E. Pendergrass, J. Org. Chem. 1981, 46, 219-220) confirmed that the concentration of denaturation initiator solution is 0.35 M.

Example 1

5 kg of n-hexane, 2.4 ml (0.35 M) of the modified polymerization initiator prepared in Preparation Example 1 were added to a 20 L autoclave reactor, and 270 g of styrene, 710 g of 1,3-butadiene and 2, as a polar additive were added thereto. After 0.75 g of 2-bis (2-oxoranyl) propane was added thereto, the temperature inside the reactor was raised to 40 ° C, and the adiabatic heating reaction was performed. After 30 minutes, 20 g of 1,3-butadiene was added to cap the polymer end with butadiene. Then, the reaction was stopped using ethanol, and 33 g of a solution of 30 wt% of Wingstay K, an antioxidant, dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified styrene-butadiene copolymer.

Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the modified polymerization initiator prepared in Preparation Example 2 was used as the modified polymerization initiator.

Example 3

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the modified polymerization initiator prepared in Preparation Example 3 was used as the modified polymerization initiator.

Example 4

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the modified polymerization initiator prepared in Preparation Example 4 was used as the modified polymerization initiator.

Example 5

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that the modified polymerization initiator prepared in Preparation Example 5 was used as the modified polymerization initiator.

Comparative Example 1

Into a 20 L autoclave reactor, 270 g of styrene, 730 g of 1,3-butadiene, 5 kg of normal hexane, 0.75 g of 2,2-bis (2-oxolanyl) propane were added as a polar additive, and the temperature inside the reactor was 40 It heated up at ° C. When the internal temperature of the reactor reached 40 ° C, 3.57 g (2.5 M in normal hexane) of n-butyllithium was added to the reactor to perform an adiabatic heating reaction. Then, the reaction was stopped using ethanol, and 33 g of a solution of 30 wt% of Wingstay K, an antioxidant, dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll dried to remove the residual solvent and water to prepare a styrene-butadiene copolymer.

Comparative Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that 2-rithio-2-phenyl-1,3-dithiane was used as the modified polymerization initiator.

Comparative Example 3

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 except that 2-rithio-2- (4-dimethylaminophenyl) -1,3-dithiane was used as the modified polymerization initiator.

Experimental Example 1

Physical properties of the modified styrene-butadiene copolymers and styrene-butadiene copolymers prepared in Examples and Comparative Examples were measured in the following manners, and the results are shown in Table 1 below.

1) Styrene derived unit and vinyl content

Styrene derived units (SM) and vinyl content in each copolymer were measured using NMR.

2) weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution

Each polymer was dissolved in tetrahydrofuran (THF) for 30 minutes under 40 ° C., and then loaded on a gel permeation chromatography (GPC) and flowed through. In this case, two columns of PLgel Olexis brand name and one PLgel mixed-C column of Polymer Laboratories were used in combination. The newly replaced columns were all mixed bed type columns, and polystyrene was used as the gel permeation chromatography standard material (GPC Standard material).

3) Mooney viscosity

For each polymer, the Mooney viscosity (MV) was measured under conditions of Rotor Speed 2 ± 0.02 rpm at 100 ° C. using a Large Rotor with Monsanto MV2000E. At this time, the sample used was left at room temperature (23 ± 3 ℃) for more than 30 minutes, and collected 27 ± 3g filled inside the die cavity and operated the platen (Platen) to measure the Mooney viscosity.

division Example Comparative example One 2 3 4 5 One 2 3 Degeneration denaturalization Undenatured denaturalization NMR
(wt%) Styrene
Origin unit 27 27 27 27 27 27 27 27 Vinyl content 43 43 43 43 43 43 43 43 GPC Results Mn (x10 ³ g / mol) 299 308 304 315 310 291 313 298 Mw (x10 ³ g / mol) 359 343 350 373 341 349 348 362 Mw / Mn 1.21 1.12 1.15 1.2 1.12 1.17 1.15 1.20 MV (ML1 + 4, @ 100 ℃) (MU) 75 73 72 74 72 71 72 73

Experimental Example 2

Rubber compositions and rubber specimens were prepared using the modified styrene-butadiene copolymers and styrene-butadiene copolymers prepared in Examples and Comparative Examples, and then the tensile, viscoelastic and abrasion resistance properties were measured in the following manner. . The results are shown in Table 2 below.

Specifically, each rubber specimen was prepared through a first stage kneading process and a second stage kneading process. In this case, the amount of the material excluding the copolymer is shown based on 100 parts by weight of the copolymer. In the first stage kneading, 137.5 parts by weight of each copolymer, 70 parts by weight of silica, and 11.2 parts by weight of bis (3-triethoxysilylpropyl) tetrasulfide as a silane coupling agent using a half-barrier with a temperature controller. 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid, 2 parts by weight of antioxidant, and 1 part by weight of wax were mixed and kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at the discharge temperature of 145 ° C to 155 ° C. In the second stage kneading, after cooling the first blend to room temperature, 1.75 parts by weight of rubber accelerator (CZ), 1.5 parts by weight of sulfur powder, and 2 parts by weight of vulcanization accelerator are added to the kneader, followed by mixing at a temperature of 100 ° C. or lower, and then A blend was obtained. Thereafter, each rubber specimen was prepared by a curing process at 100 ° C. for 20 minutes.

1) Tensile Properties

Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the specimen and the tensile stress (300% modulus) at 300% elongation. Specifically, the tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester to obtain tensile strength and tensile stress at 300% elongation. The measured value was indexed and shown as the measured value of the comparative example 1 as 100, and was shown. The higher the index, the better the physical properties.

2) viscoelastic properties

Viscoelastic properties were measured by using a dynamic mechanical analyzer (TA, Inc.) to measure Tan δ by changing the strain at a frequency of 10 Hz and measuring temperature (0 ° C. to 70 ° C.) in torsion mode. The higher the low temperature 0 ° C tanδ value in the measurement value, the better the wet road resistance, and the lower the high temperature 60 ° C tanδ value indicates less hysteresis loss and better low running resistance (fuel efficiency), but compared in Table 2 below. The measured value of Example 1 was set to 100, and each measured value was shown exponentially (%). Higher index means better viscoelastic properties.

3) wear resistance

Wear resistance was measured by applying a load of 10 N to a wear drum-coated rotating drum using a DIN wear tester and moving each rubber specimen in a direction perpendicular to the rotational direction of the drum. The rotational speed of the drum was 40 rpm, and upon completion of the test the total distance traveled was 40 m. The smaller the loss weight, the better the wear resistance. However, in Table 2, the measured value of Comparative Example 1 was set to 100, and each measured value was indexed. The higher the index, the better the wear resistance.

division Example Comparative example One 2 3 4 5 One 2 3 Tensile Properties
(Index value) 300% modulus 101 102 102 100 101 100 101 103 The tensile strength 106 106 107 110 106 100 103 104 Viscoelastic properties
(Index value) Tan δat 0 ℃ 100 102 100 101 100 100 101 100 Tan δat 60 ℃ 121 123 119 120 119 100 105 111 Wear Resistance (Index Value) 105 104 100 104 101 100 103 101

As shown in Table 2, the rubber specimen prepared using the modified styrene-butadiene copolymer of Examples 1 to 5 according to an embodiment of the present invention is unmodified or present in Comparative Examples 1 to 3 Compared to the rubber specimens prepared using the modified styrene-butadiene copolymer using a modified polymerization initiator other than the specific modified polymerization initiator in the invention, it was confirmed that the overall excellent tensile properties and workability, viscoelastic properties and wear resistance.

Specifically, Examples 1 to 5 was confirmed that the viscoelastic properties and wear resistance significantly improved compared to Comparative Example 1 which is an unmodified styrene-butadiene copolymer.

In addition, Examples 1 to 5 show excellent abrasion resistance and low temperature Tan δ characteristics equivalent or higher than those of the modified styrene-butadiene copolymers of Comparative Examples 2 and 3, in particular, among tensile and viscoelastic properties. It was confirmed that the high temperature (60 ° C.) Tan δ characteristics were greatly improved. At this time, the modified styrene-butadiene copolymers of Comparative Examples 2 and 3 are prepared under the same conditions as in Example 1 except that the structure of the modified polymerization initiator is different from that of the present invention.

Claims (17)

A modified conjugated diene-based polymer containing at least one functional group derived from a modified polymerization initiator, wherein the modified polymerization initiator is a reaction product of a compound represented by the following formula (1) with an organometallic compound:
[Formula 1]

In Chemical Formula 1,
R ₁ is hydrogen, an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with substituent X, a cycloalkyl group having 1 to 20 carbon atoms substituted or unsubstituted with substituent X, or an aryl having 6 to 30 carbon atoms unsubstituted or substituted with substituent X Gigi,
R ₂ is an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with substituent X,
R ₃ is hydrogen,
X is a substituent selected from the group consisting of a hydroxyl group (-OH), a halogen group, a primary amino group (-NH ₂ ) and a secondary amino group (-NHR '), and when X is a secondary amino group, R' is An alkyl group having 1 to 10 carbon atoms,
At least one of R ₁ and R ₂ is necessarily substituted with a substituent X.
The method according to claim 1,
In Chemical Formula 1,
R ₁ is hydrogen, an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with substituent X, or an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with substituent X,
R ₂ is a modified conjugated diene-based polymer which is an alkylene group having 1 to 3 carbon atoms unsubstituted or substituted with a substituent X.
The method according to claim 1,
The compound represented by Formula 1 is a modified conjugated diene-based polymer comprising at least one selected from the compounds represented by Formula 2 to 4:
[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,
R ₄ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms,
R ₅ to R ₁₁ are each independently hydrogen, a substituent X, or an alkyl group having 1 to 10 carbon atoms,
In Formula 2, at least one of R ₅ to R ₇ is a substituent X, In Formula 3, at least one of R ₅ to R ₉ is a substituent X, and in Formula 4, at least one of R ₅ to R ₁₁ is a substituent X ,
R ₃ and X are as defined in the formula (1).
The method according to claim 1,
The compound represented by Formula 1 is a modified conjugated diene-based polymer comprising at least one selected from the group consisting of compounds represented by the following formulas 2a, 2b, 3a, 3b, 4a and 4b:
[Formula 2a]

[Formula 2b]

[Formula 3a]

[Formula 3b]

[Formula 4a]

[Formula 4b]

In the formula 2a, 2b, 3a, 3b, 4a and 4b,
R ₄ is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms,
R _5, R _6, R ₈ and R ₉ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,
R ₃ and X are as defined in formula (1).
The method according to claim 1,
The compound represented by Formula 1 is a modified conjugated diene-based polymer comprising at least one compound of the compound represented by the formula 1-1 to 1-15:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

[Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

The method according to claim 1,
The modified conjugated diene polymer is a homopolymer of conjugated diene monomer; Or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer; a modified conjugated diene polymer.
The method according to claim 1,
The modified conjugated diene-based polymer is a modified conjugated diene-based polymer that includes a modifier-derived functional group at the other end of the polymer that is not bonded to the modified polymerization initiator.
The method according to claim 7,
The modifier is an alkoxysilane group, azacyclopropane group, ketone group, carboxyl group, thiocarboxyl group, carbonate, carboxylic anhydride, carboxylic acid metal salt, acid halide, urea group, thiourea group, amide group, thioamide group, isocyanate group, thio Containing at least one functional group selected from an isocyanate group, a halogenated isocyano group, an epoxy group, a thioethoxy group, an imine group, and a YZ bond group, wherein Y is Sn, Si, Ge or P, and Z is a halogen group Phosphorus-modified conjugated diene polymer.
The method according to claim 1,
The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 100,000 g / mol to 800,000 g / mol.
The method according to claim 1,
The polymer is a modified conjugated diene-based polymer having a molecular weight distribution (Mw / Mn) of 1.0 to 3.0.
Conjugated diene monomers in the presence of a modified polymerization initiator in a hydrocarbon solvent; Or polymerizing an aromatic vinyl monomer and a conjugated diene monomer to prepare an active polymer having the modified initiator-derived functional group introduced at least at one end thereof (step 1),
The modified polymerization initiator is a reaction product prepared by reacting a compound represented by the following formula (1) with an organometallic compound:
[Formula 1]

In Chemical Formula 1,
R ₁ is hydrogen, an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with substituent X, a cycloalkyl group having 1 to 20 carbon atoms substituted or unsubstituted with substituent X, or an aryl having 6 to 30 carbon atoms unsubstituted or substituted with substituent X Gigi,
R ₂ is an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with substituent X,
R ₃ is hydrogen,
X is a substituent selected from the group consisting of a hydroxyl group (-OH), a halogen group, a primary amino group (-NH ₂ ) and a secondary amino group (-NHR '), and when X is a secondary amino group, R' is An alkyl group having 1 to 10 carbon atoms,
At least one of R ₁ and R ₂ is necessarily substituted with a substituent X.
The method according to claim 11,
The modified polymerization initiator is a method for producing a modified conjugated diene-based polymer that is used in 0.05 to 1.0 parts by weight based on 100 parts by weight of the total monomers.
The method according to claim 11,
Method of producing a modified conjugated diene-based polymer further comprises the step of reacting the active polymer with a modifier (step 2).
The method according to claim 13,
The modifying agent is a method for producing a modified conjugated diene-based polymer that is used in a 5.0 molar ratio of 0.1 mole to 1 mole of the modified polymerization initiator.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 1 and a filler.
The method according to claim 15,
The rubber composition comprises 0.1 part by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.
The method according to claim 15,
The filler is a rubber composition comprising a silica-based filler.