KR102479146B1 - Both ends-modified diene polymer and preparation method thereof - Google Patents

Abstract

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

Description

Both ends-modified conjugated diene polymer and preparation method thereof {Both ends-modified diene polymer and preparation method thereof}

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

Recently, in accordance with the demand for low fuel consumption for automobiles, conjugated diene-based polymers having low running resistance, excellent abrasion resistance and tensile properties, and control stability represented by wet skid resistance are required as rubber materials for tires.

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

Natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known as rubber materials with low hysteresis loss, 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) are produced by emulsion polymerization or solution polymerization and are used as rubber for tires. .

Among them, the greatest advantage of solution polymerization over 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 changed by coupling or modification. that it can be controlled. Therefore, it is easy to change the structure of the finally manufactured SBR or BR rubber, and it is possible to reduce the movement of the chain ends and increase the binding force with fillers such as silica or carbon black by binding or modifying the chain ends. It is widely used as a rubber material for tires.

When such solution-polymerized SBR is used as a rubber material for tires, the glass transition temperature of the rubber can be raised by increasing the vinyl content in the SBR, thereby controlling required tire properties such as driving resistance and braking power, and properly adjusting the glass transition temperature. Adjustment can reduce fuel consumption.

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

For example, U.S. Patent No. 4,397,994 suggests a technique in which active anions at the ends of polymer chains obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, are bonded 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 the reinforcing filler, low hysteresis loss and wet skid resistance are improved. However, compared to carbon black on a hydrophobic surface, silica on a hydrophilic surface has a low affinity with rubber and has a disadvantage of poor dispersibility. Therefore, a separate silane couple is needed to improve dispersibility or to provide a bond between silica and rubber. You need to use a ring agent.

Accordingly, a method of introducing a functional group having affinity or reactivity with silica at the end of the rubber molecule has been made, but the effect is not sufficient.

Therefore, it is necessary to develop a rubber having high compatibility with fillers including silica.

US 4,397,994 A

The present invention has been made to solve the problems of the prior art, and both ends of the modified conjugated diene containing a functional group derived from a polymerization initiator and a functional group derived from a modifier have excellent affinity with a filler and thus have improved mechanical properties and viscoelastic properties. It aims at providing a system polymer.

In addition, an object of the present invention is to provide a method for producing the modified conjugated diene-based polymer.

In order to solve the above problems, the present invention provides a modified conjugated diene-based polymer including a functional group derived from a compound represented by Formula 1 at one end and a functional group derived from a modifier represented by Formula 2 at the other end. do:

[Formula 1]

In Formula 1,

R ₁ is an allyl group having 3 to 20 carbon atoms;

R ₂ and R ₃ are independently of each other 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. is a monovalent hydrocarbon group of

[Formula 2]

In Formula 2,

으로 표시되는 글리콜 유닛이되, R₅ 및 R₆ 중 적어도 하나는 글리콜 유닛이고,R ₅ and R ₆ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms; or

A glycol unit represented by, wherein at least one of R ₅ and R ₆ is a glycol unit,

R ₇ is a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms;

_R8 to R ₁₁ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms,

R ₁₂ is a divalent hydrocarbon group having 1 to 10 carbon atoms;

j and k are each independently 0 or 1, n is an integer from 1 to 10,

When R ₅ is a glycol unit, 3-il and i are each independently 1 or 2, but not 2 at the same time, l is 0 or 1;

When R ₆ is a glycol unit, i and l are each independently 1 or 2, but not 2 at the same time, and 3-il is 0 or 1;

When both R ₅ and R ₆ are glycol units, i is 1 or 2, and 1 and 3-il are independently 0 or 1 but not 0 at the same time.

In addition, the present invention comprises the steps of preparing a modified polymerization initiator by reacting a compound represented by Formula 1 with an organic alkali metal compound in a hydrocarbon solvent (step 1); preparing an active polymer having a functional group derived from the compound represented by Formula 1 bound to one end by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of the modified polymerization initiator (step 2); And it provides a method for producing the modified conjugated diene-based polymer comprising the step (step 3) of reacting the active polymer with a modifier represented by Formula 2:

[Formula 1]

In Formula 1,

R ₁ is an allyl group having 3 to 20 carbon atoms;

R ₂ and R ₃ are independently of each other 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. is a monovalent hydrocarbon group of

[Formula 2]

In Formula 2,

으로 표시되는 글리콜 유닛이되, R₅ 및 R₆ 중 적어도 하나는 글리콜 유닛이고,R ₅ and R ₆ are independently of each other a monovalent hydrocarbon group having 1 to 30 carbon atoms; or

A glycol unit represented by, wherein at least one of R ₅ and R ₆ is a glycol unit,

R ₇ is a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms;

_R8 to R ₁₁ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms,

R ₁₂ is a divalent hydrocarbon group having 1 to 10 carbon atoms;

j and k are each independently 0 or 1, n is an integer from 1 to 10,

When R ₅ is a glycol unit, 3-il and i are each independently 1 or 2, but not 2 at the same time, l is 0 or 1;

When R ₆ is a glycol unit, i and l are each independently 1 or 2, but not 2 at the same time, and 3-il is 0 or 1;

When both R ₅ and R ₆ are glycol units, i is 1 or 2, and 1 and 3-il are independently 0 or 1 but not 0 at the same time.

The modified conjugated diene-based polymer according to the present invention includes a functional group derived from a compound represented by Formula 1 at one end and a functional group derived from a modifier represented by Formula 2 at the other end, so that it has excellent affinity with fillers such as silica. It may have excellent processability, mechanical properties and viscoelasticity.

In addition, the production method according to the present invention can easily introduce a functional group derived from the compound represented by Formula 1 to one end of the polymer chain by preparing an active polymer in the presence of a modified polymerization initiator prepared using the compound represented by Formula 1 , By reacting the active polymer with the modifier represented by Formula 2, it is possible to easily introduce a functional group derived from the modifier represented by Formula 2 to the other end of the polymer chain, and as a result, a highly modified functional group introduced at both ends of the polymer chain. Modified conjugated diene-based polymers can be easily produced.

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

Terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

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

The term "alkyl group" used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl, isopropyl, sec-butyl , branched alkyl groups such as tert-butyl and neo-pentyl.

The term "alkylene group" used in the present invention may mean divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene and butylene.

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

The term "aryl group" used in the present invention may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded ( polycyclic aromatic hydrocarbon).

The terms "derived unit" and "derived functional group" used in the present invention may indicate a component or structure derived from a certain material or the material itself.

As used herein, the term "monovalent hydrocarbon group" refers to a monovalent substituent derived from a hydrocarbon group, such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group having an unsaturated bond, etc. It may represent a bonded monovalent atomic group, and the monovalent atomic group may have a linear or branched structure depending on the structure of the bond.

The term "divalent hydrocarbon group" used in the present invention refers to a divalent substituent derived from a hydrocarbon group, such as an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group containing an unsaturated bond, etc. It may represent a divalent atomic group in which carbon and hydrogen are bonded, and the divalent atomic group may have a linear or branched structure depending on the structure of the bond.

The present invention provides a modified conjugated diene-based polymer having functional groups introduced at both ends of the polymer chain and having excellent affinity with fillers, particularly silica-based fillers.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a functional group derived from a compound represented by Formula 1 below at one end and a functional group derived from a modifier represented by Formula 2 below at the other end. do.

[Formula 1]

In Formula 1,

R ₁ is an allyl group having 3 to 20 carbon atoms;

R ₂ and R ₃ are independently of each other 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. is a monovalent hydrocarbon group of

[Formula 2]

In Formula 2,

으로 표시되는 글리콜 유닛이되, R₅ 및 R₆ 중 적어도 하나는 글리콜 유닛이고,R ₅ and R ₆ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms; or

A glycol unit represented by, wherein at least one of R ₅ and R ₆ is a glycol unit,

R ₇ is a single bond or a divalent hydrocarbon group having 1 to 30 carbon atoms;

_R8 to R ₁₁ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms,

R ₁₂ is a divalent hydrocarbon group having 1 to 10 carbon atoms;

j and k are each independently 0 or 1, n is an integer from 1 to 10,

When R ₅ is a glycol unit, 3-il and i are each independently 1 or 2, but not 2 at the same time, l is 0 or 1;

When R ₆ is a glycol unit, i and l are each independently 1 or 2, but not 2 at the same time, and 3-il is 0 or 1;

When both R ₅ and R ₆ are glycol units, i is 1 or 2, and 1 and 3-il are independently 0 or 1 but not 0 at the same time.

Specifically, in Formula 1, R ₁ may be an allyl group having 3 to 20 carbon atoms, and more specifically, R ₁ may be an allyl group having 3 to 10 carbon atoms.

In Formula 1, R ₂ and R ₃ are each independently substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, or It may be an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and specifically, R ₂ and R ₃ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 12 carbon atoms. It may be an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of:

More specifically, in one embodiment of the present invention, in Formula 1, R ₁ may be an allyl group having 3 to 10 carbon atoms, and R ₂ and R ₃ are independently of each other an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. It may be an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of a cycloalkyl group and an aryl group having 6 to 12 carbon atoms.

으로 표시되는 글리콜 유닛이되, R₅ 및 R₆ 중 적어도 하나는 글리콜 유닛일 수 있다. 이때, R₅가 글리콜 유닛인 경우 3-i-l 및 i는 서로 독립적으로 1 또는 2이되 동시에 2는 아니며, l은 0 또는 1이고, R₆가 글리콜 유닛인 경우 i 및 l은 서로 독립적으로 1 또는 2이되 동시에 2는 아니며, 3-i-l은 0 또는 1이고, R₅ 및 R₆ 모두 글리콜 유닛인 경우 i는 1 또는 2이고, l 및 3-i-l은 서로 독립적으로 0 또는 1이되 동시에 0은 아닐 수 있다. 여기에서, R₁₁은 탄소수 1 내지 30의 1가 탄화수소기일 수 있고, n은 1 내지 10의 정수일 수 있다. 구체적으로, 상기 R₅ 및 R₆는 서로 독립적으로

으로 표시되는 글리콜 유닛일 수 있고, 여기에서, R₁₁은 탄소수 1 내지 10의 알킬기일 수 있고, n은 2 내지 8의 정수일 수 있다.In addition, in Formula 2, R ₅ and R ₆ are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms or

A glycol unit represented by , at least one of R ₅ and R ₆ may be a glycol unit. In this case, when R ₅ is a glycol unit, 3-il and i are each independently 1 or 2, but not 2 at the same time, l is 0 or 1, and when R ₆ is a glycol unit, i and l are independently 1 or 1 2 but not simultaneously 2, 3-il is 0 or 1, i is 1 or 2 when R ₅ and R ₆ are both glycol units, and 1 and 3-il are independently 0 or 1 but not 0 at the same time can Here, R ₁₁ may be a monovalent hydrocarbon group having 1 to 30 carbon atoms, and n may be an integer of 1 to 10. Specifically, the R ₅ and R ₆ are independently of each other

It may be a glycol unit represented by , wherein R ₁₁ may be an alkyl group having 1 to 10 carbon atoms, and n may be an integer of 2 to 8.

Further, in Formula ₂ , R ₇ may be a single bond or a divalent hydrocarbon group having 1 to ₃₀ carbon atoms. 20 alkylene groups; arylene groups having 6 to 20 carbon atoms such as phenylene groups; Or, as a combination thereof, it may be an arylalkylene group having 7 to 20 carbon atoms. Specifically, R ₇ may be an alkylene group having 1 to 10 carbon atoms.

In addition, in Formula 2, R ₈ to R ₁₀ may be each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms, specifically, 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 a carbon atom having 7 to 20 carbon atoms. It may be selected from the group consisting of an arylalkyl group of, and more specifically, may be an alkyl group having 1 to 10 carbon atoms independently of each other.

Also, in Formula 2, R ₁₂ may be a divalent hydrocarbon group having 1 to 10 carbon atoms, and specifically, may be an alkylene group having 2 to 6 carbon atoms.

으로 표시되는 글리콜 유닛이고, R₇은 탄소수 1 내지 10의 알킬렌기이며, R₈ 내지 R₁₁은 서로 독립적으로 탄소수 1 내지 10의 알킬기이고, R₁₂는 탄소수 2 내지 6의 알킬렌기이며, i는 1 또는 2의 정수이고, 3-i-l 및 l은 서로 독립적으로 0 또는 1의 정수이되 동시에 0은 아니고, n은 2 내지 8의 정수인 것일 수 있다.More specifically, in Formula 2 in one embodiment of the present invention, R ₅ and R ₆ are

A glycol unit represented by, R ₇ is an alkylene group having 1 to 10 carbon atoms, R ₈ to R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms, R ₁₂ is an alkylene group having 2 to 6 carbon atoms, i is an integer of 1 or 2, and 3-il and l are independently an integer of 0 or 1. but not 0 at the same time, and n may be an integer from 2 to 8.

으로 표시되는 글리콜 유닛이고, R₇은 탄소수 1 내지 10의 알킬렌기이며, R₈ 내지 R₁₁은 서로 독립적으로 탄소수 1 내지 10의 알킬기이고, R₁₂는 탄소수 2 내지 6의 알킬렌기이며, i는 1 또는 2의 정수이고, 3-i-l 및 l은 서로 독립적으로 0 또는 1의 정수이되 동시에 0은 아니고, n은 4 내지 8의 정수인 것일 수 있다. 이 경우, 이의 유래 작용기를 포함하는 변성 공액디엔계 중합체의 인장특성 및 점탄성 특성이 더 크게 우수할 수 있다.More specifically, in Formula 2 in one embodiment of the present invention, R ₅ and R ₆ are

A glycol unit represented by, R ₇ is an alkylene group having 1 to 10 carbon atoms, R ₈ to R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms, R ₁₂ is an alkylene group having 2 to 6 carbon atoms, i is an integer of 1 or 2, and 3-il and l are independently an integer of 0 or 1. but not 0 at the same time, n may be an integer from 4 to 8. In this case, the tensile properties and viscoelastic properties of the modified conjugated diene-based polymer including functional groups derived therefrom may be significantly superior.

More specifically, in one embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by Formula 1-1 below.

[Formula 1-1]

In one embodiment of the present invention, the modifier represented by Formula 2 is N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxyhexadecane- 16-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-2,5,8,11,14-pentaoxyhexadecane-16-amine, N,N-bis(2- (2-(2-methoxyethoxy)ethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine, N,N-bis(2-(2-(2-butoxyethoxy) Ethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanona Decan-1-amine, N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl) Propan-1-amine, N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-N-(3-(trimethoxysilyl)propyl)butan-1-amine, N-( 3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecane-1-amine, N-(3, 6,9,12,15-pentaoxanonadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanonadecan-1-amine, or N, It may be N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15,18-hexaoxodocosan-1-amine. Preferably, the modifier represented by Formula 2 is N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxyhexadecane-16-amine, N, N-bis(3-(diethoxy(methyl)silyl)propyl)-2,5,8,11,14-pentaoxyhexadecane-16-amine, N,N-bis(2-(2-(2-) Methoxyethoxy)ethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine, N,N-bis(2-(2-(2-butoxyethoxy)ethoxy)ethyl)- 3-(triethoxysilyl)propan-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanonadecan-1-amine, N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecane-1-amine, N- (3,6,9,12,15-pentaoxanonadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanonadecan-1-amine; or N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15,18-hexaoxodocosan-1-amine.

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

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

The modified conjugated diene-based polymer according to an embodiment of the present invention has a tertiary amine group, which is a functional group derived from a compound represented by Formula 1, at one end and a tertiary amine group, which is a functional group derived from a modifier represented by Formula 2, at the other end, It may include an alkylene glycol group and an alkoxysilane group. The tertiary amine group can prevent aggregation between fillers by interfering with hydrogen bonding between hydroxyl groups present on the surface of the filler, thereby improving the dispersibility of the filler. In addition, the alkylene glycol group can improve the processability of the polymer by increasing the affinity between the polymer chain and the filler, and the alkoxysilane group condenses with a functional group on the surface of the filler, for example, a silanol group on the surface of silica when the filler is silica. By reacting, the abrasion resistance and processability of the polymer can be improved.

Therefore, the modified conjugated diene-based polymer according to an embodiment of the present invention includes a compound-derived functional group represented by Formula 1 and a modifier-derived functional group represented by Formula 2, so that it may have excellent affinity with fillers, particularly silica, , Therefore, the compounding properties with the filler can be excellent, so that the processability of the rubber composition containing the modified conjugated diene-based polymer can be improved, and as a result, the tensile strength and abrasion resistance of a molded article manufactured using the rubber composition, such as a tire, can be improved. and viscoelastic 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 1,000,000 g/mol, specifically 400,000 g/mol to 700,000 g/mol.

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

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1.0 to 3.0. Specifically, the molecular weight distribution may be 1.0 to 2.0.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention has the above molecular weight distribution range and weight when considering the good balance improvement effect of 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 simultaneously satisfy the above-mentioned range conditions.

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 1,500,000 g / mol, and a number average molecular weight of 100,000 g / mol to 1,000,000 g / mol , More specifically, it may have a polydispersity of 2.0 or less, a weight average molecular weight of 500,000 g/mol to 1,200,000 g/mol, and a number average molecular weight of 400,000 g/mol to 700,000 g/mol.

Here, the weight average molecular weight and number average molecular weight are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution (Mw/Mn) is also called polydispersity, and the weight average molecular weight (Mw) It was calculated as the ratio (Mw/Mn) to the number average molecular weight (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% to 50% by weight, and the glass transition temperature when the vinyl content is in the above range Since can be adjusted within an appropriate range, when applied to tires, physical properties required for tires such as driving resistance and braking power are excellent, and fuel consumption is reduced.

At this time, the vinyl content represents the content of 1,2-added conjugated diene-based monomers rather than 1,4-added with respect to 100% by weight of the conjugated diene-based polymer composed of a monomer having a vinyl group or a conjugated diene-based monomer.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a polymer having high linearity having a -S/R (stress/relaxation) value of 0.7 or more at 100 °C. At this time, -S/R represents a change in stress in response to the same amount of strain generated in the material, and is an index representing the linearity of the polymer. Generally, the lower the -S/R value, the lower the linearity of the polymer, and the lower the linearity, the higher the rolling resistance or rolling resistance when applied to a rubber composition. In addition, the degree of branching and molecular weight distribution of the polymer can be predicted from the -S / R value, and the lower the -S / R value, the higher the degree of branching and the wider the molecular weight distribution. As a result, the processability of the polymer is excellent, while the mechanical characteristics are low.

As described above, the modified conjugated diene-based polymer according to an embodiment of the present invention has a high -S/R value of 0.7 or more at 100 ° C., so when applied to a rubber composition, resistance characteristics and fuel consumption characteristics may be excellent. Specifically, the -S / R value of the modified conjugated diene-based polymer may be 0.7 to 1.2.

Here, the -S / R value was measured using a Mooney viscometer, for example, a large rotor of Monsanto's MV2000E under conditions of 100 ° C and a rotor speed of 2 ± 0.02 rpm. Specifically, after leaving the polymer at room temperature (23 ± 5 ° C) for more than 30 minutes, 27 ± 3 g was taken and filled into the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen, Additionally, the -S/R value was obtained by measuring the slope value of the Mooney viscosity change that appears as the torque was released for 1 minute.

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

The preparation method according to an embodiment of the present invention comprises the steps of preparing a modified polymerization initiator by reacting a compound represented by Formula 1 with an organic alkali metal compound in a hydrocarbon solvent (step 1); preparing an active polymer having a functional group derived from the compound represented by Formula 1 bound to one end by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of the modified polymerization initiator (step 2); and a step (step 3) of reacting the active polymer with a modifier represented by Formula 2 below.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, R ₁ to R ₃ , R ₅ to R ₁₀ , 3-il, i, l, j and k are as defined in the modified conjugated diene-based polymer.

Step 1 is a step for preparing a modified polymerization initiator including a unit derived from the compound represented by Formula 1, and may be performed by reacting the compound represented by Formula 1 with an organic alkali metal compound in a hydrocarbon solvent.

In this case, the compound represented by Formula 1 and the organic alkali metal compound may be reacted in a molar ratio of 1:0.8 to 3. If the compound represented by Formula 1 and the organic alkali metal compound are reacted in the above ratio, the unit derived from the compound represented by Formula 1 and the unit derived from the organic alkali metal compound are easily bonded to each other to obtain a modified polymerization initiator with optimal performance. can form Accordingly, a functional group derived from the compound represented by Formula 1 may be introduced to one end of the polymer chain while easily forming an active polymer in step 2 described later. Here, the bond may indicate that the metal component derived from the organic alkali metal compound is ionic bonded to the carbon of the unit derived from the compound represented by Formula 1.

The organic alkali metal compound is, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naph Tyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , It may be at least one selected from the group consisting of lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide. Specifically, the organic alkali metal compound may be n-butyllithium.

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

Meanwhile, when reacting the compound represented by Chemical Formula 1 with an organic alkali metal compound, a polar additive may be added if necessary. At this time, when a polar solvent is added, the polar solvent may be used in an amount of 0.5 to 1.1 equivalents relative to 1 equivalent of the organic alkali metal compound. In addition, the polar solvent is not particularly limited, but may be, for example, at least one selected from the group consisting of trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, specifically tetramethylethylenediamine. there is.

In addition, the reaction of step 1 may be carried out at 50 ° C to 70 ° C for 20 minutes to 30 minutes.

Step 2 is a step for preparing an active polymer in which a functional group derived from the compound represented by Formula 1 is introduced at one end. It can be carried out by polymerizing the based monomers.

The conjugated diene-based monomer is not particularly limited, but examples include 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 a conjugated diene-based monomer and an aromatic vinyl-based monomer are used together as the monomer, the conjugated diene-based monomer contains 60% by weight or more of the conjugated diene-based monomer-derived unit in the finally prepared modified conjugated diene-based polymer, specifically, It may be used in an amount comprised between 60% by weight and less than 100% by weight, more specifically 60% by weight to 85% by weight.

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

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

The modified polymerization initiator may be used in an amount of 0.05 to 0.3 parts by weight based on 100 g of the total monomers.

The polymerization of step 2 may be performed by adding more polar additives if necessary, and the polar additives may be added in an amount of 0.001 part by weight to 10 parts by weight based on 100 parts by weight of the total monomers. Specifically, 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 may be added.

The polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylenedimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethyl It may be one or more selected from the group consisting of aminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine.

The manufacturing method according to an embodiment of the present invention compensates for the difference in reaction rate between the conjugated diene-based monomer and the aromatic vinyl-based monomer when copolymerizing the conjugated diene-based monomer and the aromatic vinyl-based monomer by using the polar additive so as to easily form a random copolymer. can induce

In addition, the polymerization of step 2 may be elevated temperature polymerization, isothermal polymerization or constant temperature polymerization (adiabatic polymerization).

Here, the constant temperature polymerization refers to a polymerization method comprising the step of polymerizing with the reaction heat itself without optionally applying heat after initiating the polymerization, and the elevated temperature polymerization refers to a polymerization method in which the temperature is increased by arbitrarily applying heat after the initiation of the polymerization. The isothermal polymerization represents a polymerization method in which heat is applied to increase heat or heat is taken away to keep the temperature of the polymerized product constant after the polymerization is initiated.

The polymerization may be carried out at a temperature range of -20 ° C to 200 ° C, specifically at 20 ° C to 150 ° C, more specifically at a temperature range of 30 ° C to 120 ° C for 15 minutes to 3 hours can If, when carried out in the above temperature range, the polymerization reaction can be easily controlled, and the polymerization reaction rate and efficiency can be excellent.

Step 3 is a step for preparing a modified conjugated diene-based polymer, and may be performed by reacting the active polymer with the modifier represented by Formula 2. At this time, step 3 may be a denaturation reaction step.

Specifically, the modifier represented by Chemical Formula 2 may be used in an amount of 0.8 to 1.5 moles based on 1 mole of the modified polymerization initiator.

If the modifier is used in an amount within the above ratio range, a modification reaction with optimal performance can be performed, and a conjugated diene-based polymer with a high modification rate can be obtained.

The reaction of step 3 according to an embodiment of the present invention is a modification reaction for introducing a functional group into a polymer, and the reaction may be carried out at a temperature range of 10 ° C to 120 ° C for 10 minutes to 5 hours.

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

After completion of the above-described modification reaction, the polymerization reaction may be stopped by adding an ethylene or isopropanol solution to the polymerization reaction system. Thereafter, the modified conjugated diene-based polymer may be obtained through desolvation treatment such as steam stripping to lower the partial pressure of the solvent through supply of steam or vacuum drying treatment. In addition, among the reaction products obtained as a result of the above modification reaction, an unmodified active polymer may be included together with the above modified conjugated diene polymer.

The manufacturing method according to an embodiment of the present invention may further include one or more post-process steps of recovering and drying the solvent and unreacted monomers as necessary after step 3, wherein the post-process step is, for example, the reaction product It may be carried out by putting it in hot water heated by steam, stirring to remove the solvent, and roll drying to remove the residual amount of solvent and water.

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

In the rubber composition according to an embodiment of the present invention, the modified conjugated diene-based polymer is contained in an amount of 0.1 wt% or more and 100 wt% or less, specifically, 10 wt% to 100 wt%, and more specifically, 20 wt% to 90 wt%. may include If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, the effect of improving the abrasion resistance and crack resistance of a molded product manufactured using the rubber composition, for example, 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 component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, it may be included in 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be natural rubber or synthetic rubber, for example, 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, halogenated butyl rubber, and the like, and any one or a mixture of two or more of these may be used.

In addition, the rubber composition may include 0.1 part 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 be silica-based, carbon black, or a combination thereof. Specifically, the filler may be carbon black.

The carbon black-based filler is not particularly limited, but may have, for example, a nitrogen adsorption specific surface area (N ₂ SA, measured in accordance with JIS K 6217-2: 2001) of 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. If the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² /g, the processability of the rubber composition may deteriorate, and if it is less than 20 m ² /g, the reinforcing performance of the carbon black may be insignificant. In addition, if the DBP oil absorption amount of the carbon black exceeds 200 cc/100g, the processability of the rubber composition may deteriorate, and if the DBP oil absorption amount is less than 80 cc/100g, 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 (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be wet room silica, which has the most remarkable effect of improving fracture characteristics and the effect of combining wet grip. In addition, the silica has a nitrogen adsorption specific surface area per gram (N ₂ SA) of 120 m 2 / g to 180 m 2 / g, and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 100 m 2 / g to 200 m 2 It can be /g. If the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, there is a fear that the reinforcing performance by silica may decrease, and if it exceeds 180 m 2 /g, the processability of the rubber composition may decrease. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m 2 / g, there is a possibility that the reinforcing performance by the silica filler may decrease, and if it exceeds 200 m 2 / g, the processability of the rubber composition may decrease.

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

The silane coupling agent is specifically 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-dimethylthiocarbamoyltetrasul Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide and the like, and any one or a mixture of two or more of these may be used. More specifically, considering the effect of improving reinforcement, the silane coupling agent 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 having a functional group having high affinity with the filler introduced into the active site is used as a rubber component, the amount of the silane coupling agent is It can be reduced more 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 within the above range, 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 an amount of 5 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 a sulfur powder, and may be included in an amount of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the necessary elastic modulus and strength of the vulcanized rubber composition, and at the same time, it is possible to obtain 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-scorch agents, zinc white ), stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The vulcanization accelerator is not particularly limited, specifically M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. A thiazole-based compound of or a guanidine-based compound such as DPG (diphenylguanidine) may be used. The vulcanization accelerator may be included in an amount of 0.1 part 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, it may be a paraffinic, naphthenic, or aromatic compound, and more specifically, considering tensile strength and abrasion resistance, aromatic process oil is a And considering low-temperature characteristics, naphthenic or paraffinic process oils may be used. 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, and when included in the above amount, it is possible to prevent a decrease in tensile strength and low heat generation (low fuel consumption) of vulcanized rubber.

In addition, the anti-aging agent is specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- Toxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, and the like are exemplified. The antioxidant 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, or an internal mixer according to the above compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of a tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, cheifer, or bead coated rubber, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture of various industrial rubber products.

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

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are for exemplifying the present invention, and the scope of the present invention is not limited only to these.

Preparation Example 1: Preparation of N-allyl-N-butylbutan-1-amine (N-allyl-N-butylbutan-1-amine)

Acetyl was added to the reactor, 2.25 g (0.454 mole) of potassium hydroxide was added thereto, and then 70 ml (0.415 mole) of dibutylamine was added dropwise. Thereafter, 39 ml (0.451 mol) of allyl bromide was slowly added dropwise at 0° C., and reacted at room temperature for 10 hours or more under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed under reduced pressure after filtering. Then, after dissolving in ethyl acetate, impurities were removed with distilled water, and the organic layer was dried over anhydrous magnesium sulfate, and solids were removed using a filter. In addition, the organic solvent was removed under reduced pressure to obtain 37.5 g (yield: 53.3%) of liquid N-allyl-N-butylbutan-1-amine. The obtained N-allyl-N-butylbutan-1-amine was confirmed through nuclear magnetic resonance spectroscopy ( ¹ H NMR).

¹ H NMR (500 MHz, CDCl ₃ ): δ 5.88-5.80 (m, 1H), 5.15-5.06 (m, 2H), 3.06-3.05 (d, J=6.5, 2H), 2.4-2.37 (t, J =7.75, 4H), 1.43–1.37 (m, 4H), 1.31–1.23 (m, 4H), 0.90–0.87 (t, 6H).

Preparation Example 2: N, N-bis (3- (triethoxysilyl) propyl) -3,6,9,12,15-pentaoxanonadecan-1-amine (N, N-bis (3- (triethoxysilyl) Preparation of )propyl)-3,6,9,12,15-pentaoxanonadecan-1-amine)

300 ml of acetonitrile in which 144.03 g (338.32 mmol) of bis(3-(triethoxysilyl)propyl)amine was dissolved was added to the reactor, and 102.7 g (1014.96 mmol) of triethylamine was added thereto and stirred. Thereafter, 200 ml of acetonitrile in which 198.95 g (405.9 mmol) of 3,6,9,12,15-pentaoxanonadecyl 4-methylbenzenesulfonate was dissolved was added, and the mixture was stirred for 12 hours while heating to 80°C. Thereafter, the volatile solvent was removed under reduced pressure, the residue was extracted with hexane, and the hexane was removed by distillation under reduced pressure to obtain N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12, 183.40 g (248.5 mmol, 73% yield) of a bright yellow oil of 15-pentaoxanonadecan-1-amine were obtained. The obtained N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanonadecan-1-amine was analyzed by ¹ H nuclear magnetic resonance spectroscopy (1 H NMR) confirmed through

¹ H NMR (500 MHz, CDCl ₃ ): δ 3.83-3.79 (q, 12H), 3.65-3.63 (m, 16H), 3.58-3.56 (m, 4H), 3.46-3.43 (t, 2H), 3.08- 3.04 (m, 4H), 1.79-1.69 (m, 4H), 1.58-1.53 (m, 2H), 1.39-1.33 (m, 2H), 1.23-1.20 (t, 18H), 0.92-0.89 (t, 3H) ), 0.60–0.58 (t, 4H).

Preparation Example 3: N, N-bis (3- (triethoxysilyl) propyl) -2,5,8,11,14-pentaoxahexadecane-1-amine (N, N-bis (3- (triethoxysilyl) Preparation of )propyl)-2,5,8,11,14-pentaoxahexadecan-1-amine)

50 ml of acetonitrile in which 48.8 g (120 mmol) of 2,5,8,11,14-pentaoxahexadecan-16-yl 4-methinebenzenesulfonate was dissolved was added to the reactor, and 20.2 g of triethylamine was added thereto. (200 mmol) was added and stirred. Thereafter, 50 ml of acetonitrile in which 42.5 g (100 mmol) of bis(3-(triethoxysilyl)propyl)amine was dissolved was added, and the mixture was stirred for 12 hours while heating to 70°C. Thereafter, the volatile solvent was removed under reduced pressure, the residue was extracted with hexane, and the hexane was removed by distillation under reduced pressure to obtain N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11, This gave 46.9 g (71 mmol, 71% yield) of a bright yellow oil of 14-pentaoxahexadecane-1-amine. The obtained N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-1-amine was analyzed by ¹ H nuclear magnetic resonance spectroscopy (1 H NMR) confirmed through

¹ H NMR (500 MHz, CDCl ₃ ): δ 3.81 (q, 12H), 3.66-3.52 (m, 18H), 3.38 (s, 3H), 2.66 (dd, 2H), 2.45 (dd, 4H), 1.53 (m, 4H), 1.22 (t, 18H), 0.57 (dd, 4H).

Preparation Example 4: N,N-bis(3-(diethoxy(methyl)silyl)propyl)-2,5,8,11,14-pentaoxahexadecane-1-amine (N,N-bis(3- Preparation of (diethoxy(methyl)silyl)propyl)-2,5,8,11,14-pentaoxahexadecan-1-amine)

50 ml of acetonitrile in which 97.6 g (240 mmol) of 2,5,8,11,14-pentaoxahexadecan-16-yl 4-methinebenzenesulfonate was dissolved was added to the reactor, and 40.5 g of triethylamine was added thereto. (400 mmol) was added and stirred. Thereafter, 50 ml of acetonitrile in which 73.1 g (200 mmol) of bis(3-(diethoxy(methyl)silyl)propyl)amine was dissolved was added, and the mixture was stirred for 16 hours while heating to 70°C. Thereafter, the volatile solvent was removed under reduced pressure, the residue was extracted with hexane, and the hexane was removed by distillation under reduced pressure to obtain N,N-bis(3-(diethoxy(methyl)silyl)propyl)-2,5,8, 90.0 g (150 mmol, 75% yield) of a bright yellow oil of 11,14-pentaoxahexadecan-1-amine were obtained. The obtained N,N-bis(3-(diethoxy(methyl)silyl)propyl)-2,5,8,11,14-pentaoxahexadecane-1-amine showed a ¹ H nuclear magnetic resonance spectroscopy spectrum (1H NMR) was confirmed.

¹ H NMR (500 MHz, CDCl ₃ ): δ 3.76 (q, 8H), 3.65-3.52 (m, 18H), 3.38 (s, 3H), 2.66 (dd, 2H), 2.45 (dd, 4H), 1.49 (m, 4H), 1.22 (t, 12H), 0.55 (dd, 4H), 0.11 (s, 6H).

Preparation Example 5: N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane- Preparation of 1-amine (N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine)

25 ml of acetonitrile in which 21.3 g (50 mmol) of bis(3-(triethoxysilyl)propyl)amine was dissolved was put into the reactor, and 10.45 g (75 mmol) of triethylamine was added thereto and stirred. Then, 25 ml of acetonitrile in which 19.1 g (60 mmol) of 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate was dissolved was added and heated to 70°C for 24 hours. Stir. Thereafter, the volatile solvent was removed under reduced pressure, the residue was extracted with hexane, and the hexane was distilled off under reduced pressure to obtain N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3-( This gave 20.0 g (41 mmol, 70% yield) of a light yellow oil of triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine. Obtained N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane-1- The amine was confirmed through ¹ H nuclear magnetic resonance spectroscopy (1 H NMR).

¹ H NMR (500 MHz, CDCl ₃ ): δ 3.81 (q, 12H), 3.65-3.51 (m, 10H), 3.38 (s, 3H), 2.66 (dd, 2H), 2.45 (dd, 4H), 1.54 (m, 4H), 1.22 (t, 18H), 0.56 (dd, 4H).

Preparation Example 6: N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-N-(3-(triethoxysilyl)propyl)butan-1-amine (N-(2- Preparation of (2-(2-methoxyethoxy)ethoxy)ethyl)-N-(3-(triethoxysilyl)propyl)butane-1-amine)

30 ml of acetonitrile in which 14.1 g (60 mmol) of N-(3-(triethoxysilyl)propyl)butan-1-amine was dissolved was put into the reactor, and 9.1 g (90 mmol) of triethylamine was added thereto. and stirred. Thereafter, 30 ml of acetonitrile in which 22.9 g (72 mmol) of 2-(2-(2-methoxyethoxy)ethoxy)ethyl 4-methylbenzenesulfonate was dissolved was added and heated to 70°C for 24 hours. Stir. Thereafter, the volatile solvent was removed under reduced pressure, the residue was extracted with hexane, and the hexane was distilled off under reduced pressure to obtain N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-N-( This gave 16.9 g (44.4 mmol, 74% yield) of a light yellow oil of 3-(triethoxysilyl)propyl)butan-1-amine. The obtained N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-N-(3-(triethoxysilyl)propyl)butan-1-amine was analyzed by ¹ H nuclear magnetic resonance spectroscopy. It was confirmed through a spectrum (1H NMR).

¹ H NMR (500 MHz, CDCl ₃ ): δ 3.57 (s, 9H), 3.61-3.45 (m, 10H), 3.36 (s, 3H), 2.59 (t, 2H), 2.49 (m, 4H), 1.58 (m, 2H), 1.40 (m, 2H), 1.25 (m, 2H), 0.91 (t, 3H), 0.56 (dd, 2H).

Example 1

In a 20 L autoclave reactor, 2 kg of n-hexane, 2.11 g of N-allyl-N-butylbutan-1-amine prepared in Preparation Example 1 and 160 g of n-butyllithium (0.5 wt% in n-hexane), A modified polymerization initiator was prepared by adding 1.45 g of tremethylethylenediamine (TMEDA) and reacting at 60° C. for 30 minutes. Here, 3 kg of n-hexane, 270 g of styrene, 710 g of 1,3-butadiene, and 1.1 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, and then the initial temperature (60℃) was insulated. The temperature rise reaction proceeded. After 30 minutes, 20 g of 1,3-butadiene was added to cap the end of the polymer with butadiene, and after 10 minutes, the N,N-bis (3-(triethoxy Silyl) propyl) -3,6,9,12,15-pentaoxanonadecan-1-amine was added and reacted for 15 minutes ([DTP] / [act. Li] = 1.5: 1 molar ratio, [denaturant] /[act.Li]=1:1 molar ratio). Then, the reaction was stopped using ethanol, and 33 g of a solution in which 30% by weight of Wingstay K, an antioxidant, was dissolved in hexane was added. The polymer obtained as a result was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove residual solvent and water to prepare a modified styrene-butadiene copolymer.

Example 2

In Example 1, prepared instead of N, N-bis (3- (triethoxysilyl) propyl) -3,6,9,12,15-pentaoxanonadecan-1-amine prepared in Preparation Example 2 Example 1, except that the N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine prepared in Example 3 was added. A modified styrene-butadiene copolymer was prepared in the same manner as described above.

Example 3

In Example 1, prepared instead of N, N-bis (3- (triethoxysilyl) propyl) -3,6,9,12,15-pentaoxanonadecan-1-amine prepared in Preparation Example 2 Carried out except that N, N-bis (3- (diethoxy (methyl) silyl) propyl) -2,5,8,11,14-pentaoxahexadecane-16-amine prepared in Example 4 was added. A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1.

Example 4

In Example 1, prepared instead of N, N-bis (3- (triethoxysilyl) propyl) -3,6,9,12,15-pentaoxanonadecan-1-amine prepared in Preparation Example 2 N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl-3-(triethoxysilyl)-N-(3-triethoxysilyl)propyl)propane-1 prepared in Example 5 - A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that amine was added.

Comparative Example 1

After adding 270 g of styrene, 710 g of 1,3-butadiene, and 5 kg of n-hexane, and 1.41 g of 2,2-bis(2-oxolanyl)propane as a polar additive to a 20 L autoclave reactor, the temperature inside the reactor was measured. The temperature was raised to 60°C. When the internal temperature of the reactor reached 60° C., 96 g (0.5 wt% in n-hexane) of n-butyllithium was introduced into the reactor to perform an adiabatic temperature raising reaction. After 30 minutes, 20 g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. Then, the reaction was stopped using ethanol, and 33 g of a solution in which 30% by weight of Wingstay K, an antioxidant, was dissolved in hexane was added. The polymer obtained as a result was put in hot water heated by steam, stirred to remove the solvent, and then roll dried to remove the remaining solvent and water to prepare a styrene-butadiene copolymer.

Comparative Example 2

After adding 270 g of styrene, 710 g of 1,3-butadiene and 5 kg of n-hexane, and 1.79 g of 2,2-bis(2-oxolanyl)propane as a polar additive to a 20 L autoclave reactor, the temperature inside the reactor was measured. The temperature was raised to 60°C. When the internal temperature of the reactor reached 60° C., 118 g (0.5 wt% in n-hexane) of n-butyllithium was introduced into the reactor to perform an adiabatic temperature raising reaction. After 30 minutes, 20 g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. Then, N, N-bis (3- (triethoxysilyl) propyl) -3,6,9,12,15-pentaoxanonadecan-1-amine prepared in Preparation Example 2 was added as a denaturant for 15 minutes ([DTP] / [act. Li] = 1.5: 1 molar ratio, [denaturant] / [act. Li] = 1: 1 molar ratio). Then, the reaction was stopped using ethanol, and 33 g of a solution in which 30% by weight of Wingstay K, an antioxidant, was dissolved in hexane was added. The polymer obtained as a result was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove residual solvent and water to prepare a modified styrene-butadiene copolymer.

Experimental Example 1

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

1) Styrene-derived units and vinyl content

Styrene-derived unit (SM) and vinyl contents 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 a condition of 40° C., and then loaded and flowed through gel permeation chromatography (GPC). At this time, two columns of PLgel Olexis and one column of PLgel mixed-C from Polymer Laboratories were used in combination. In addition, all of the newly replaced columns used a mixed bed type column, and polystyrene was used as a standard material for gel permeation chromatography (GPC standard material).

3) Mooney viscosity (PMV: polymer MV) and -S/R value

For each polymer, Mooney viscosity (MV) was measured at 100° C. using a large rotor with MV2000E manufactured by Monsanto under the conditions of a rotor speed of 2±0.02 rpm. The sample used at this time was left at room temperature (23 ± 3 ° C) for more than 30 minutes, then 27 ± 3 g was taken and filled into the die cavity, and Mooney viscosity was measured while applying torque by operating a platen.

In addition, when measuring the Mooney viscosity, the change in Mooney viscosity that appears as the torque is released was observed for 1 minute, and the -S/R value was determined from the slope value.

division Example comparative example One 2 3 4 One 2 denaturation Sock hem degeneration undenatured Sock hem degeneration NMR
(wt%) Styrene
unit of origin 27.4 27.3 27.4 27.3 27.1 27.1 vinyl content 46.5 46.8 46.5 46.7 45.3 47.2 GPC result Mn (x10 ⁵ g/mol) 5.94 5.81 5.72 6.02 5.44 6.07 Mw(x10 ⁵ g/mol) 10.17 10.06 9.82 9.62 6.01 9.58 Mw/Mn 1.71 1.73 1.72 1.60 1.10 1.58 PMV(ML1+4, @100℃) (MU) 86.5 87.1 84.8 86.2 82.6 84.6

As shown in Table 1, the modified styrene-butadiene copolymer of Example prepared using the modified polymerization initiator according to one embodiment of the present invention is similar to Comparative Example 1 prepared using n-butyllithium as the polymerization initiator. Compared to the modified styrene-butadiene copolymer, it was confirmed to have a similar microstructure (styrene-derived unit and vinyl content). This indicates that the modified polymerization initiator according to an embodiment of the present invention easily worked as a polymerization initiator.

Experimental Example 2

After preparing rubber compositions and rubber specimens using the modified styrene-butadiene copolymers and styrene-butadiene copolymers prepared in Examples and Comparative Examples, Mooney viscosity, tensile properties, viscoelastic properties and wear resistance were measured by the following methods. each was measured. The results are shown in Table 2 below.

Specifically, each rubber specimen was manufactured through a first-stage kneading process and a second-stage kneading process. At this time, the amount of material used 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 of the above copolymers, 70 parts by weight of silica, and 11.2 parts by weight of bis(3-triethoxysilylpropyl)tetrasulfide as a silane coupling agent were used in a semi-barrier mixer equipped with a temperature control device. 2 parts by weight of anti-aging agent (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 blended and kneaded. At this time, the temperature of the kneader was controlled and the primary mixture was obtained at a discharge temperature of 145 ° C to 155 ° C. In the second stage kneading, after cooling the first mixture to room temperature, 1.75 parts by weight of a rubber accelerator (CZ), 1.5 parts by weight of sulfur powder, and 2 parts by weight of a vulcanization accelerator were added to a kneading machine and mixed at a temperature of 100 ° C or less to obtain a second a mixture was obtained. Thereafter, each rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

1) Mooney viscosity (CMV: compound MV)

Processability characteristics were compared and analyzed by measuring the Mooney viscosity of each secondary compound obtained during the preparation of the rubber specimen. At this time, the lower the Mooney viscosity measurement value, the better the workability characteristics.

Mooney viscosity was measured using a large rotor with Monsanto's MV2000E under the condition of a rotor speed of 2 ± 0.02 rpm at 100 ° C. The sample used at this time was left at room temperature (23 ± 3 ° C) for more than 30 minutes, then 27 ± 3 g was taken and filled into the die cavity, and Mooney viscosity was measured while applying torque by operating a platen.

2) Tensile properties

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

3) Viscoelastic properties

For viscoelastic properties, Tan δ was measured by changing strain at a frequency of 10 Hz and each measurement temperature (0 ° C to 70 ° C) in torsion mode using a dynamic mechanical analyzer (TA). Tanδ at 0°C represents wet grip, and tanδ at 60°C represents fuel economy. The measured value was represented by indexing the measured value of Comparative Example 1 to 100.

4) Wear resistance

For abrasion resistance, a load of 10 N was applied to a rotating drum with an abrasion paper attached using a DIN abrasion tester, and each rubber specimen was moved in a direction perpendicular to the rotational direction of the drum, and then the abraded weight loss was measured. The rotational speed of the drum was 40 rpm, and the total moving distance of the specimen upon completion of the test was 40 m. The smaller the weight loss, the better the abrasion resistance. The measured value was represented by indexing the measured value of Comparative Example 1 to 100.

division Example comparative example One 2 3 4 One 2 CMV (ML1+4, @100℃) (MU) 77.0 77.3 77.2 82.1 83.0 78.3 tensile properties 300% modulus (kgf/cm ² ) 144.3 143.2 141.3 132.5 114.2 131.1 Tensile strength (kgf/cm ² ) 186.7 190.8 189.7 188.1 187.3 187.0 Viscoelastic properties Tan δat 0℃ 111 109 108 105 100 106 Tan δat 60℃ 123 119 121 113 100 116 wear resistance 109 107 105 106 100 105

As shown in Table 2, the rubber specimens prepared using the styrene-butadiene copolymer modified at both ends of Examples 1 to 4 according to an embodiment of the present invention were unmodified in Comparative Examples 1 to 4 Or, it was confirmed that the viscoelastic property and abrasion resistance were excellent as compared to the rubber specimen prepared using the modified styrene-butadiene copolymer, and overall tensile properties and compounding processability were excellent.

Specifically, Examples 1 to 3 had superior tensile properties and greatly improved viscoelastic properties and wear resistance compared to Comparative Example 1, which is an unmodified styrene-butadiene copolymer, as well as Mooney viscosity (CMV) of the vulcanized compound. From the greatly reduced, it was confirmed that the blending processability was also remarkably excellent.

In addition, it was confirmed that Examples 1 to 3 exhibited excellent tensile properties and wear resistance that were equal to or better than Comparative Example 2, which is a terminal styrene-butadiene copolymer, and particularly greatly improved viscoelastic properties.

On the other hand, Example 4 has improved tensile properties, viscoelastic properties and wear resistance compared to Comparative Example 1, but the effect is significantly reduced compared to other Examples 1 to 3. At this time, Example 4 is different from other Example 1 to Example 3, it is prepared using a modifier having a shorter glycol unit length (a compound having n = 3 in Formula 2), and through this, when n = 4 or more in Formula 2, viscoelastic properties, particularly fuel economy at 60 ° C. This result indicates that Tan δ can be greatly improved.

Claims (13)

A modified conjugated diene-based polymer comprising a modified polymerization initiator-derived functional group including a compound-derived unit represented by Formula 1 at one end and a modifier-derived functional group represented by Formula 2 at the other end:
[Formula 1]

In Formula 1,
R ₁ is an allyl group having 3 to 20 carbon atoms;
R ₂ and R ₃ are independently of each other 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. is a monovalent hydrocarbon group of
[Formula 2]

In Formula 2,
R ₅ and R ₆ are independently of each other

A glycol unit represented by
R ₇ is an alkylene group having 1 to 10 carbon atoms;
_R8 to R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms,
R ₁₂ is an alkylene group having 2 to 6 carbon atoms;
i is an integer of 1 or 2;
j and k are independently 0 or 1;
3-il and l are independently of each other an integer of 0 or 1, but not 0 at the same time;
n is an integer from 4 to 8;
The method of claim 1,
In Formula 1,
R ₁ is an allyl group having 3 to 10 carbon atoms;
R ₂ and R ₃ are independently of each other 1 to 10 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms. A modified conjugated diene-based polymer that is an alkyl group of.
delete The method of claim 1,
The compound represented by Formula 1 is a modified conjugated diene-based polymer that is a compound represented by Formula 1-1:
[Formula 1-1]

The method of claim 1,
The modifier represented by Formula 2 is N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxyhexadecane-16-amine, N,N-bis( 3-(diethoxy(methyl)silyl)propyl)-2,5,8,11,14-pentaoxyhexadecane-16-amine, N,N-bis(3-(triethoxysilyl)propyl)-3 ,6,9,12,15-pentaoxanonadecan-1-amine, N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3 ,6,9,12-tetraoxahexadecane-1-amine, N-(3,6,9,12,15-pentaoxanonandecyl)-N-(3-(triethoxysilyl)propyl)- 3,6,9,12,15-pentaoxanonandecane-1-amine, or N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15,18-hexa A modified conjugated diene-based polymer that is oxodokosan-1-amine.
The method of claim 1,
The modified conjugated diene-based polymer may be a homopolymer of a conjugated diene-based monomer; Or a modified conjugated diene-based polymer that is a modified polymer of a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer.
The method of claim 1,
The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 100,000 g / mol to 1,000,000 g / mol.
The method of claim 1,
The polymer is a modified conjugated diene-based polymer having a molecular weight distribution (Mw / Mn) of 1.0 to 3.0.
1) preparing a modified polymerization initiator by reacting a compound represented by Formula 1 with an organic alkali metal compound in a hydrocarbon solvent;
2) polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of the modified polymerization initiator to prepare an active polymer having a functional group derived from the compound represented by Formula 1 bound to one end thereof; and
3) A method for producing a modified conjugated diene-based polymer according to claim 1, comprising reacting the active polymer with a modifier represented by Formula 2 below:
[Formula 1]

In Formula 1,
R ₁ is an allyl group having 3 to 20 carbon atoms;
R ₂ and R ₃ are independently of each other 1 to 20 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms. is a monovalent hydrocarbon group of
[Formula 2]

In Formula 2,
R ₅ and R ₆ are independently of each other

A glycol unit represented by
R ₇ is an alkylene group having 1 to 10 carbon atoms;
_R8 to R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms,
R ₁₂ is an alkylene group having 2 to 6 carbon atoms;
i is an integer of 1 or 2;
j and k are independently 0 or 1;
3-il and l are each independently 0 or 1, but not 0 at the same time;
n is an integer from 4 to 8;
The method of claim 9,
The organic alkali metal compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyl Lithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, A modified conjugated diene-based polymer of at least one selected from the group consisting of lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide manufacturing method.
The method of claim 9,
A method for producing a modified conjugated diene-based polymer wherein the compound represented by Formula 1 and the organic alkali metal compound are reacted in a molar ratio of 1:0.8 to 3.
The method of claim 9,
The method for producing a modified conjugated diene-based polymer in which the modifier represented by Formula 2 is used in an amount of 0.8 to 1.5 moles relative to 1 mole of the modified polymerization initiator.
The method of claim 9,
The polymerization of step 2) is performed by adding a polar additive,
The polar additive is a method for producing a modified conjugated diene-based polymer that is added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomer.