KR102308724B1 - Modified conjugated diene polymer and method for preparing the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer, and more particularly, through a condensation reaction between a compound capable of a condensation reaction with an unreacted alkoxy group present at the terminal of the modified conjugated diene-based polymer after the modification process, an unreacted alkoxy group It relates to a modified conjugated diene-based polymer having excellent processability by suppressing increase in Mooney viscosity and excellent interaction with an inorganic filler, a method for preparing the same, and a rubber composition comprising the same.

Description

Modified conjugated diene-based polymer and manufacturing method thereof

The present invention relates to a modified conjugated diene-based polymer, and more particularly, through a condensation reaction between a compound capable of a condensation reaction with an unreacted alkoxy group present at the terminal of the modified conjugated diene-based polymer after the modification process, an unreacted alkoxy group It relates to a modified conjugated diene-based polymer having excellent processability by suppressing increase in Mooney viscosity and excellent interaction with an inorganic filler, a method for preparing the same, and a rubber composition comprising the same.

In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet road resistance is required as a rubber material for tires.

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

As a rubber material with a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low resistance to wet road surfaces. Accordingly, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends, and to increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

When this solution-polymerized SBR is used as a rubber material for a tire, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to control the required physical properties of the tire such as running resistance and braking force, and the glass transition temperature can be lowered. By properly adjusting it, fuel consumption can be reduced. The solution polymerization SBR is prepared using an anionic polymerization initiator, and the chain ends of the formed polymer are bound or modified using various modifiers. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is combined using a binder such as a tin compound. did.

On the other hand, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as reinforcing fillers, there are advantages in that low hysteresis loss and wet road resistance are improved. However, compared to carbon black on the hydrophobic surface, silica on the hydrophilic surface has a disadvantage in that it has poor dispersibility due to low affinity with rubber. It is necessary to use a ring agent. Accordingly, a method has been made to introduce a functional group having affinity or reactivity with silica at the end of the rubber molecule, but the effect is not sufficient. There is a problem that workability is lowered.

US 4397994 A

The present invention has been devised to solve the problems of the prior art, and through a condensation reaction between a compound capable of a condensation reaction with an unreacted alkoxy group present at the terminal of a modified conjugated diene-based polymer after the modification process, the unreacted alkoxy group An object of the present invention is to provide a modified conjugated diene-based polymer having excellent processability by suppressing increase in Mooney viscosity and excellent interaction with an inorganic filler, a method for preparing the same, and a rubber composition including the same.

According to one embodiment of the present invention for solving the above problems, the present invention includes a repeating unit derived from a conjugated diene-based monomer, and a first modifier-derived linking group comprising a compound represented by the following Chemical Formula 1 or 2 at one end It provides a modified conjugated diene-based polymer comprising a functional group derived from a second modifier comprising a compound represented by the following formula (3):

[Formula 1]

In Formula 1, R ¹ to R ³ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, 5 to 30 carbon atoms of a cycloalkyl group, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms, wherein ^{2 or more of R 1} to R ³ may be an alkoxy group having 1 to 30 carbon atoms, and R ⁴ is 1 to 10 carbon atoms of an alkyl group; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or it may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms,

[Formula 2]

In Formula 2, R ⁵ to R ¹⁰ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, 5 to 30 carbon atoms. of a cycloalkyl group, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms of a heterocyclic group, or a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms, and at ^{least 2 of R 5} to R ¹⁰ may be an alkoxy group having 1 to 30 carbon atoms, and R ¹¹ is It may be one type of hetero atom selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms including N, O and S atoms, or N, O and S atoms, and R ¹¹ is O , or in the case of an S atom, R ¹² may not be present, and R ¹² is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or it may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms, and o and p may each independently be 0, or an integer of 1 to 20,

[Formula 3]

In Formula 3, R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or it may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms, and F ¹ to F ⁴ are each independently hydrogen, an epoxy group, a carboxy group, an acryloyl group, a cyano group, an isocyanate group, a carbon number 1 to 30 alkyl group, C 2 to C 30 alkenyl group, C 2 to C 30 alkynyl group, C 5 to C 30 cycloalkyl group, or C 6 to C 30 aryl group, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one atom, an epoxy group, a carboxy group, an acryloyl group, a cyano group, an isocyanate group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, a cycloalkyl group having 6 to carbon atoms It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with an aryl group of 30, a heterocyclic group having 3 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms, and n may be an integer of 1 to 10.

In addition, the present invention is a hydrocarbon solvent, in the presence of an organometallic compound, by polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer to prepare an active polymer to which an organic metal is bonded (S1); preparing a first modified conjugated diene-based polymer by reacting the active polymer with a first modifier comprising a compound represented by Formula 1 or Formula 2 below (S2); and reacting the first modified conjugated diene-based polymer with a second modifier comprising a compound represented by the following Chemical Formula 3 (S3).

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3, the definition of each substituent is as defined above.

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

According to the present invention, after the modification process through the first modifier, a condensation reaction with the unreacted alkoxy group of the functional group derived from the first modifier present at the terminal of the first modified conjugated diene-based polymer is possible, and as a rigid structure, the solution rubber polymerization phase When an additional modification reaction is performed by adding a second modifier including a compound having a structure capable of achieving uniform distribution by input, Mooney viscosity increase due to unreacted alkoxy groups present in the first modified conjugated diene-based polymer is increased. By suppressing it, the processability of the modified conjugated diene-based polymer is excellent, and the modified conjugated diene-based polymer includes a functional group derived from the second modifier having a hard structure, thereby performing a strength compensation function similar to that of the filler.

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

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

The modified conjugated diene-based polymer according to the present invention includes a repeating unit derived from a conjugated diene-based monomer, and a first modifier-derived linking group including a compound represented by the following Chemical Formula 1 or 2 at one end thereof, and a compound represented by the following Chemical Formula 3 It may include a functional group derived from a second denaturant comprising a.

[Formula 1]

In Formula 1, R ¹ to R ³ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, 5 to 30 carbon atoms of a cycloalkyl group, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms, wherein ^{2 or more of R 1} to R ³ may be an alkoxy group having 1 to 30 carbon atoms, and R ⁴ is 1 to 10 carbon atoms of an alkyl group; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or it may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms.

As a specific example, in Formula 1, R ¹ to R ³ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. , R ¹ to R ³ necessarily at least 2 may be an alkoxy group ^{having 1 to 10 carbon atoms, R 4} is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms, including to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a carbon number It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a 4 to 10 heteroaryl group.

As a more specific example, in Formula 1, R ¹ to R ³ are each independently an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and at ^{least 2 of R 1} to R ³ must have 1 to 10 carbon atoms. may be an alkoxy group of, R ⁴ is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms, including 3 to 3 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a 4 to 10 heteroaryl group.

[Formula 2]

In Formula 2, R ⁵ to R ¹⁰ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, 5 to 30 carbon atoms. of a cycloalkyl group, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, 3 to 30 carbon atoms of a heterocyclic group, or a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms, and at ^{least 2 of R 5} to R ¹⁰ may be an alkoxy group having 1 to 30 carbon atoms, and R ¹¹ is It may be one type of hetero atom selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms including N, O and S atoms, or N, O and S atoms, and R ¹¹ is O , or in the case of an S atom, R ¹² may not be present, and R ¹² is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or it may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms, and o and p may each independently be 0, or an integer of 1 to 20.

As a specific example, in Formula 2, R ⁵ to R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or , C1 to C10 alkyl group, C5 to C10 cycloalkyl group, C6 to C10 aryl group, C3 to C10 heterocyclic group, or C4 to C10 heteroaryl group substituted with 1 to 10 carbon atoms is a hydrocarbon group, but necessarily 2 or more of ^{R 5} to R ^{10 may be an alkoxy group having 1 to 10 carbon atoms, R 11} is an alkylene group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms including N, O and S atoms It may be a heteroalkylene group or one hetero atom selected from the group consisting of N, O and S atoms, and when R ¹¹ is O or S, R ¹² may not be present, and R ¹² has 1 to 10 carbon atoms. of an alkyl group; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms, including to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a carbon number It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group of 4 to 10, and o and p may each independently be 0, or an integer of 1 to 10.

As a more specific example, in Formula 2, R ⁵ to R ¹⁰ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heterocycle having 3 to 10 carbon atoms. or a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a group or a heteroaryl group having 4 to 10 carbon atoms, wherein at ^{least 2 of R 5} to R ¹⁰ may be an alkoxy group having 1 to 10 carbon atoms, and R ¹¹ is N, O And it may be one kind of hetero atom selected from the group consisting of ^{S atoms, when R 11} is O or an S atom, R ¹² may not be present, and R ¹² is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. 1 of 1 to 10 carbon atoms substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a heteroaryl group having 4 to 10 carbon atoms. may be a hydrocarbon group, and o and p may each independently be 0 or an integer of 1 to 10.

[Formula 3]

In Formula 3, R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or it may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms, and F ¹ to F ⁴ are each independently hydrogen, an epoxy group, a carboxy group, an acryloyl group, a cyano group, an isocyanate group, a carbon number 1 to 30 alkyl group, C 2 to C 30 alkenyl group, C 2 to C 30 alkynyl group, C 5 to C 30 cycloalkyl group, or C 6 to C 30 aryl group, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one atom, an epoxy group, a carboxy group, an acryloyl group, a cyano group, an isocyanate group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, a cycloalkyl group having 6 to carbon atoms It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with an aryl group of 30, a heterocyclic group having 3 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms, and n may be an integer of 1 to 10.

As a specific example, in Formula 3, R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms, including to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a carbon number It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a 4 to 10 heteroaryl group, and F ¹ to F ⁴ are each independently hydrogen, an epoxy group, a carboxy group, an acryloyl group, a cyano group, or an isocyanate group, or a carbon number 1 to 10 alkyl groups; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. a monovalent hydrocarbon group having 1 to 10 carbon atoms, including It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with an aryl group, a heterocyclic group having 3 to 10 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms, and n may be an integer of 1 to 10.

As a more specific example, in Formula 3, R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. 1 of 1 to 10 carbon atoms substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a heteroaryl group having 4 to 10 carbon atoms. may be a hydrocarbon group, and F ¹ to F ⁴ are each independently hydrogen, an epoxy group, a carboxy group, an acryloyl group, a cyano group, or an isocyanate group, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. or a monovalent hydrocarbon group having 1 to 10 carbon atoms including 3 to 3, an epoxy group, a carboxy group, an acryloyl group, a cyano group, an isocyanate group, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or 4 carbon atoms It may be a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group of 30 to n, and n may be an integer of 1 to 10.

As another example, in Formula 1, R ⁴ , in Formula 2, R ¹² , and in Formula 3, R ¹³ to R ¹⁶ are each independently one selected from the group consisting of a functional group represented by the following Formulas 4 to 12 may be a substituent, and in Formula 2, R ⁵ to R ¹⁰ may each independently be a substituent which is a functional group represented by Formula 11 or 12 below, and in Formula 3, F ¹ to F ⁴ are each independently each of the following Formulas It may be one kind of substituent selected from the group consisting of functional groups represented by 4 to 14.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In Formulas 4 to 14, * may mean a bonding position, TMS may be a trimethylsilyl group, Et may be an ethyl group, and R ¹⁷ to R ²⁰ are each independently 1 to 30 carbon atoms, or 1 carbon atom. to 10 alkyl groups.

In the present invention, the term 'substitution' may mean that a functional group, atomic group, or hydrogen of a compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, a functional group, atomic group, or compound One or two or more plural substituents may be present depending on the number of hydrogens present therein, and when a plurality of substituents are present, each substituent may be the same as or different from each other.

In the present invention, the term 'hetero atom' may mean an organic atom, such as nitrogen (N), oxygen (O), sulfur (S), phosphorus (P), and silicon (Si), excluding carbon and hydrogen atoms. .

In the present invention, the term 'monovalent hydrocarbon group' refers to a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group. and the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined according to the type of each substituent. In addition, when the monovalent hydrocarbon group includes one or more hetero atoms, it may mean a monovalent hydrocarbon group in which carbon atoms (excluding carbon atoms at the terminal) in the monovalent hydrocarbon group are substituted with one or more hetero atoms.

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

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

In the present invention, the term 'alkylsilyl group' may include monoalkylsilyl, dialkylsilyl, and trialkylsilyl.

In the present invention, the term 'alkenyl group' may refer to an alkyl group including one or two or more double bonds.

In the present invention, the term 'alkynyl group' may refer to an alkyl group including one or two or more triple bonds.

In the present invention, the term 'alkoxy group' may include all functional groups, atomic groups, or compounds in which hydrogen at the end of an alkyl group is substituted with an oxygen atom, such as methoxy, ethoxy, propoxy and butoxy.

In the present invention, the term 'cycloalkyl group' may be meant to include all cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons including one or two or more unsaturated bonds.

In the present invention, the term 'aryl group' 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. It may mean including all hydrocarbons.

In the present invention, the term 'heterocyclic group' may refer to a cyclic saturated or unsaturated aliphatic compound including one or more hetero atoms.

In the present invention, the term 'heteroaryl group' may refer to a cyclic aromatic compound including one or more hetero atoms.

According to an embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by the following Chemical Formulas 1-1 to 1-2.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 to 1-2, Me may be a methyl group.

According to an embodiment of the present invention, the compound represented by Chemical Formula 2 may be a compound represented by the following Chemical Formulas 2-1 to 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 to 2-2, Me may be a methyl group.

According to an embodiment of the present invention, the compound represented by Chemical Formula 3 may be a compound represented by the following Chemical Formula 3-1.

[Formula 3-1]

In Formula 3-1, Me may be a methyl group, Et may be an ethyl group, and n may be an integer of 1 to 10, 2 to 8, or 4 to 6.

As described above, according to the present invention, after the conjugated diene-based polymer is first modified from the first modifier containing the compound represented by Formula 1 or 2, the first modified conjugated diene-based polymer is present at the end of the first modified polymer. A second modifier containing a compound having a structure in which the functional group derived from the modifier can undergo a condensation reaction with the unreacted alkoxy group, and is introduced into the solution rubber polymerization phase as a hard structure to achieve a uniform distribution, is added to carry out an additional modification reaction. When carried out, the increase in Mooney viscosity due to unreacted alkoxy groups present in the first modified conjugated diene-based polymer is suppressed, the processability of the modified conjugated diene-based polymer is excellent, and the modified conjugated diene-based polymer is derived from a second modifier having a rigid structure Including functional groups, it is possible to perform a strength compensation function similar to that of a filler.

In the present invention, the repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the conjugated diene-based monomer is, for example, 1,3-butadiene, 2,3-dimethyl- 1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom. ) may be at least one selected from the group consisting of.

On the other hand, the modified conjugated diene-based copolymer may be, for example, a copolymer further comprising a repeating unit derived from an aromatic vinyl monomer together with the repeating unit derived from the conjugated diene-based monomer.

The repeating unit derived from the aromatic vinyl monomer may mean a repeating unit formed during polymerization of the aromatic vinyl monomer, and the aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 4-propyl. It may be at least one selected from the group consisting of styrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene.

When the modified conjugated diene-based polymer is a copolymer including repeating units derived from an aromatic vinyl monomer, the modified conjugated diene-based polymer contains 50 to 95 wt%, 55 to 90 wt%, or 60 to 95 wt% of the conjugated diene-based monomer-derived repeating unit. 90% by weight, 5 to 50% by weight, 10 to 45% by weight, or 10 to 40% by weight of the repeating unit derived from the aromatic vinyl monomer, within this range, excellent in rolling resistance, wet road resistance and abrasion resistance It works.

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

The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 10,000 g/mol to 2,000,000 g/mol, 50,000 g/mol to 1,500,000 g/mol, 100,000 g/mol to 1,000,000 g/mol mol, or 100,000 g/mol to 800,000 g/mol, and a weight average molecular weight (Mw) of 10,000 g/mol to 5,000,000 g/mol, 50,000 g/mol to 3,000,000 g/mol, 100,000 g/mol to 2,500,000 g /mol, or 150,000 g/mol to 2,000,000 g/mol, there is an excellent effect of rolling resistance and wet road resistance within this range. As another example, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1 to 5, 1 to 4, or 1.5 to 3, and within this range, an excellent balance between physical properties is obtained.

As another example, the modified conjugated diene-based polymer may have a Mooney viscosity of 40 to 110 at 100° C., and has excellent processability and productivity within this range.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 10% by weight or more, or 10% to 90% by weight, and within this range, the glass transition temperature can be adjusted to an appropriate range, so that rolling resistance, wet road resistance and excellent low fuel efficiency. Here, the vinyl content means the content of the 1,2-added conjugated diene-based monomer, not the 1,4-added, based on 100% by weight of the conjugated diene-based copolymer consisting of a monomer having a vinyl group and an aromatic vinyl-based monomer. can

Meanwhile, in the present invention, the terms 'derived repeating unit', 'derived functional group', and 'derived linking group' may refer to a component, structure, or substance itself derived from a certain substance. Specifically, in the present invention, the 'derived repeating unit' may mean a repeating unit in a polymer derived from the monomer through a polymerization reaction between the monomers, and the 'derived functional group' is one end of the polymer and the first modifier. The first modifier is present at one end of the polymer in the form of substitution, addition, or addition reaction between the liver or between the functional group derived from the first modifier and the second modifier, or the second modifier is substituted, added, or added. , or may refer to a state in which a functional group derived from the first denaturant is bonded or coupled in an added form, and the 'derived linking group' is a first present by substitution, addition, or addition reaction between the active polymer and the first denaturant. A functional group derived from a denaturant is bonded or coupled by a substitution, addition, or addition reaction with the second denaturant, so that the polymer and the second denaturant are bonded to or coupled to one first denaturant with the first denaturant as the center. It may mean a ring state, and may mean that a linking group between the polymer and the functional group derived from the second modifier present at one end of the polymer is derived from the first modifier.

The method for producing a modified conjugated diene-based polymer according to the present invention is prepared by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of an organometallic compound to prepare an organic metal-bonded active polymer step (S1); preparing a first modified conjugated diene-based polymer by reacting the active polymer with a first modifier comprising a compound represented by Formula 1 or Formula 2 below (S2); and reacting the first modified conjugated diene-based polymer with a second modifier comprising a compound represented by Formula 3 below (S3).

[Formula 1]

[Formula 2]

[Formula 3]

Definitions for each substituent of Formulas 1 to 3 are as defined above.

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.

According to an embodiment of the present invention, the compound represented by Formula 1 may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.

According to an embodiment of the present invention, the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol based on 100 g of the total monomer.

The organometallic 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-tolylllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and may be at least one selected from the group consisting of lithium isopropylamide.

Meanwhile, the polymerization in step (S1) may be carried out including a polar additive, and the polar additive may be added in an amount of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on 100 g of the total monomer. have. In addition, the polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane , bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethylether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine may be at least one selected from the group consisting of, preferably triethyl It may be an amine or tetramethylethylenediamine, and may be the same as or different from the polar additive that may be added during the preparation of the aminosilane-based compound, and when the polar additive is included, a conjugated diene-based monomer or a conjugated diene-based monomer and In the case of copolymerizing the aromatic vinyl-based monomers, there is an effect of compensating for a difference in their reaction rates, thereby inducing easy formation of a random copolymer.

The polymerization in step (S1) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by an anion-based growth polymerization reaction. In addition, the polymerization in step (S1) may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes a step of polymerization by its own heat of reaction without optionally applying heat after the organometallic compound is added. It may mean a polymerization method to increase the temperature, the temperature rise polymerization may mean a polymerization method to increase the temperature by optionally adding heat after the addition of the organometallic compound, the isothermal polymerization is heat after adding the organometallic compound It may refer to a polymerization method in which the temperature of the polymer is maintained constant by increasing heat by adding or taking heat away. In addition, the polymerization of step (S1) is, for example, the polymerization may be carried out in a temperature range of -20 °C to 200 °C, 0 °C to 150 °C, or 10 °C to 120 °C.

The active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bound.

According to an embodiment of the present invention, the molar ratio of the denaturant including the compound represented by Chemical Formula 1 or 2 and the organometallic compound may be 1:0.1 to 1:10, and within this range, the denaturation reaction of optimal performance can be performed. It can be carried out to obtain a conjugated diene-based polymer having a high modification rate.

The reaction of step (S2) is a modification reaction for introducing a functional group derived from the modifier into the active polymer, and the reaction may be performed at 0° C. to 90° C. for 1 minute to 5 hours.

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

According to an embodiment of the present invention, the first modified conjugated diene-based polymer prepared in step (S2) includes a first modifier-derived functional group bonded to one end of the polymer, and the first modifier-derived functional group has carbon atoms. It may include one or more alkoxy groups having 1 to 30 carbon atoms, or 1 to 3 alkoxy groups having 1 to 10 carbon atoms. It may serve as a reaction site for

According to an embodiment of the present invention, the reaction of the first modified conjugated diene-based polymer and the second modifier in the step (S3) is a reactor in which the reaction in step (S2) is completed, and after the reaction in step (S2) is completed, the second 1 A separate reactor to which the modified conjugated diene-based polymer is transferred, or a stripper for performing a stripping process for recovery and solvent removal of unreacted monomers after the reaction of the first modified conjugated diene-based polymer is completed can be carried out in When the step (S3) is carried out in the stripper, the second modifier may be added in the form of an additive during the stripping process, and in this case, the second modifier is evenly distributed and condensed with the first modified conjugated diene-based polymer at an appropriate ratio. There is an effect that the reaction proceeds.

On the other hand, the method for producing a modified conjugated diene-based polymer of the present invention may include a step of pre-treating the second modifier prior to the step (S3). In the pretreatment, prior to reacting the second modifier with the first modified conjugated diene-based polymer, the condensation reaction between the second modifier and the alkoxy group of the first modifier-derived functional group present at one end of the first modified conjugated diene-based polymer As a step for improving reactivity, it may include stirring _{the second modifier and water (H 2 O).} As described above, when the second modifier and water are stirred, the alkoxy group present in the second modifier is substituted with a hydroxyl group, thereby improving the reactivity of the condensation reaction.

According to the present invention, there is provided a rubber composition comprising the modified conjugated diene-based polymer.

The rubber composition may include the modified conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and an excellent balance between the physical properties.

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. As a specific example, the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-) propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc. have.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving the breaking properties and wet Wet silica may be the most excellent in compatibility with wet grip. In addition, the rubber composition may further include a carbon black-based filler if necessary.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide , bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) propyl) tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, as a rubber component, a modified conjugated diene-based polymer in which a functional group with high affinity for silica is introduced is used as a rubber component, so the compounding amount of the silane coupling agent is a common may be reduced than the case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of silica, and within this range, the effect as a coupling agent is not significant. It has the effect of preventing the gelation of the rubber component while being sufficiently exhibited.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. It has an excellent effect.

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

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. Naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, etc., may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

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

In addition, the present invention provides a tire manufactured using the rubber composition.

The tire may include a tire or a tire tread.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Example 1

In a 20 L autoclave reactor, 27 g of styrene, 73 g of 1,3-butadiene and 600 g of n-hexane, and 0.13 g of DTP (2,2-di(2-tetrahydrofuryl)propane) as a polar additive were put into the reactor, and the internal temperature of the reactor was heated to 40 °C. When the internal temperature of the reactor reached 35° C., 1.1 mmol of n-butyllithium was added to the reactor to proceed with adiabatic temperature increase. After 30 minutes after the adiabatic temperature rise reaction was completed, 2 g of 1,3-butadiene was added, and the end of the polymer was capped with butadiene. After 10 minutes, 0.11 g (0.62 mmol) of the compound represented by the following formula 1-1 was added and reacted for 20 minutes. Then, the polymerization reaction was stopped using distilled water, and then 1.87 g (0.62 mmol) of the compound represented by the following Chemical Formula 3-1 was added, followed by reaction for 30 minutes. Thereafter, 45 ml of a solution in which an antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated by steam, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water to prepare a modified conjugated diene-based polymer.

[Formula 1-1]

[Formula 3-1]

Example 2

In Example 1, 1.87 g (0.62 mmol) of the compound represented by Formula 3-1 was added to hot water heated with steam and stirred to remove the solvent, not before stopping the polymerization reaction, except that it was added It was carried out in the same manner as in Example 1.

Example 3

In Example 1, it was carried out in the same manner as in Example 1, except that 0.22 g (0.38 mmol) of the compound represented by the following formula 2-1 was added instead of the compound represented by the formula 1-1.

[Formula 2-1]

Example 4

In Example 3, 1.87 g (0.62 mmol) of the compound represented by Formula 3-1 was added to hot water heated with steam and stirred to remove the solvent before stopping the polymerization reaction, except that it was added. It was carried out in the same manner as in Example 3.

Comparative Example 1

In Example 1, it was carried out in the same manner as in Example 1, except that the compound represented by Formula 1-1 and the compound represented by Formula 3-1 were not added.

Comparative Example 2

In Example 1, except that the compound represented by Formula 1-1 was not added, it was carried out in the same manner as in Example 1.

Comparative Example 3

It was carried out in the same manner as in Example 1, except that in Example 1, the compound represented by Formula 3-1 was not added.

Comparative Example 4

Example 3 was carried out in the same manner as in Example 1, except that the compound represented by Formula 3-1 was not added.

Experimental Example 1

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

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through gel permeation chromatohraph (GPC) analysis, and molecular weight distribution (MWD, Mw/Mn) was obtained by calculating from each of the measured molecular weights. Specifically, the GPC used a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and all newly replaced columns were mixed bed type columns, When calculating molecular weight, GPC standard material was performed using PS (polystyrene).

The Mooney viscosity (MV, (ML1+4, @100°C) MU) was measured using MV-2000 (ALPHA Technologies) at 100°C at 100°C, Rotor Speed 2±0.02 rpm, Large Rotorfmf, and the sample used at this time was left at room temperature (23±3℃) for more than 30 minutes, and then collected 27±3 g, filled it in the die cavity, and operated the platen to measure for 4 minutes.

division Example comparative example One 2 3 4 One 2 3 4 Mw (X10 ³ g/mol) 300 320 400 420 176 360 380 490 Mn (X10 ³ g/mol) 250 270 310 330 160 240 260 340 MWD 1.2 1.2 1.3 1.3 1.1 1.5 1.5 1.4 MV 45 48 55 60 20 48 52 65

As shown in Table 1, Examples 1 to 4 according to an embodiment of the present invention exhibited reduced or equivalent Mooney viscosity compared to the modified Comparative Examples 2 to 4, particularly in Examples and Example 3 confirmed that Mooney viscosity was significantly reduced as compared with Comparative Example 3 and Comparative Example 4, respectively. In this case, Comparative Examples 3 and 4 were modified conjugated diene-based polymers prepared under the same conditions as Examples 1 and 3, respectively, except that the compound represented by Formula 3-1 was not used, respectively. It can be seen that the Mooney viscosity increase can be suppressed by including the functional group derived from the second denaturant according to an embodiment of the present invention.

Experimental Example 2

In order to compare and analyze the physical properties of the rubber composition containing each modified or unmodified conjugated diene-based copolymer prepared in Examples and Comparative Examples and molded articles prepared therefrom, tensile properties, abrasion resistance and wet road resistance were measured respectively. The results are shown in Tables 2 and 3 below.

1) Preparation of rubber composition

Each rubber composition was prepared through a first-stage kneading and a second-stage kneading process. In this case, the amount of the material other than the modified or unmodified conjugated diene-based polymer is shown based on 100 parts by weight of the modified or unmodified conjugated diene-based polymer. In the first stage kneading, 137.5 parts by weight of each of the modified conjugated diene-based copolymers, 70 parts by weight of silica, and bis(3-triethoxysilylpropyl)tetrasulfur as a silane coupling agent using a Banvari mixer with a temperature control device. 11.2 parts by weight of feed, 25 parts by weight of process oil (TDAE), 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid, and 1 part by weight of wax kneaded. At this time, the temperature of the kneader was controlled and the first formulation was obtained at a discharge temperature of 145 to 155 °C. In the second stage kneading, after cooling the first compound 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 are added to a kneader and mixed at a temperature of 100° C. or less to secondary A formulation was obtained. Thereafter, each rubber composition was prepared through a curing process at 100° C. for 20 minutes.

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 the time of cutting the test piece and the tensile stress (300% modulus) at 300% elongation were measured. Specifically, tensile properties were measured using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester at room temperature at a rate of 50 cm/min to obtain tensile strength and tensile stress values at 300% elongation.

3) Viscoelastic properties

For the viscoelastic properties, Tan δ was measured by changing the strain at a frequency of 10 Hz and each measurement temperature (-60 to 60°C) in torsion mode using a dynamic mechanical analyzer (TA). The higher the low temperature 0℃ Tan δ, the better the wet road resistance, and the lower the high temperature 60℃ Tan δ, the less the hysteresis loss and the better the low rolling resistance (fuel efficiency).

division Example One 2 3 4 CMB MV (ΔMV) 70 73 78 85 Tensile properties 300% modulus (kgf/cm ² ) 96 98 99 98 Tensile strength (kgf/cm ² ) 190 192 193 195 Viscoelastic properties tan δ@0℃ 0.195 0.198 0.200 0.198 tan δ@60℃ 0.120 0.121 0.118 0.119

division comparative example One 2 3 4 CMB MV 40 82 85 90 Tensile properties 300% modulus (kgf/cm ² ) 75 80 90 92 Tensile strength (kgf/cm ² ) 160 170 185 188 Viscoelastic properties tan δ@0℃ 0.175 0.188 0.193 0.195 tan δ@60℃ 0.135 0.130 0.125 0.122

In Tables 2 and 3, CMB represents the first formulation as a compound master batch, and the Mooney viscosity of CMB was measured in the same manner as described above.

As shown in Tables 2 and 3, in Examples 1 to 4 according to an embodiment of the present invention, CMB Mooney viscosity was lower than Comparative Examples 2 to 4, and through this, the It was confirmed that the Mooney viscosity increase was suppressed by the modified conjugated diene-based polymer according to an embodiment by including a functional group derived from the second modifier.

In addition, both the tensile properties and the viscoelastic properties of Examples 1 to 4 were superior to those of Comparative Examples 1 to 4, indicating that the modified conjugated diene-based polymer according to an embodiment of the present invention has excellent compounding processability. will be.

Claims (18)

Containing a repeating unit derived from a conjugated diene-based monomer,
A modified conjugated diene-based polymer comprising a first denaturant-derived linking group including a compound represented by the following Chemical Formula 1 or 2 at one end, and a second denaturant-derived functional group including a compound represented by the following Chemical Formula 3:
[Formula 1]

In Formula 1,
R ¹ to R ³ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and a cycloalkyl group having 5 to 30 carbon atoms. 6 to 30 aryl group, or a heteroaryl group having 4 to 30 carbon atoms, R ¹ to R ^{3 or} more is necessarily an alkoxy group having 1 to 30 carbon atoms,
R ⁴ is one kind of substituent selected from the group consisting of functional groups represented by the following formulas 4 to 12,
[Formula 2]

In Formula 2,
R ⁵ to R ¹⁰ are each independently an alkoxy group having 1 to 30 carbon atoms, wherein ^{at least one substituent among the substituents of R 5} to R ¹⁰ is a functional group represented by the following formula 11 or 12,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms including N, O and S atoms, or one hetero atom selected from the group consisting of N, O and S atoms, and R ¹¹ is In the case of O, or an S atom, R ¹² is absent,
R ¹² is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms,
o and p are each independently 0, or an integer from 1 to 20,
[Formula 3]

In Formula 3,
R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,
an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. or a monovalent hydrocarbon group having 1 to 10 carbon atoms and containing at least one atom,
Monovalent having 1 to 10 carbon atoms substituted with an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, or a heteroaryl group having 4 to 30 carbon atoms a hydrocarbon group,
F ¹ to F ⁴ are each independently one kind of substituent selected from the group consisting of functional groups represented by the following Chemical Formulas 4 to 14,
n is an integer from 1 to 10,
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In Formulas 4 to 14,
* is a bonding position, TMS is a trimethylsilyl group, Et is an ethyl group, and R ¹⁷ to R ²⁰ are each independently an alkyl group having 1 to 30 carbon atoms. According to claim 1,
In Formula 1,
R ¹ to R ³ are, each independently, be one having 1 to 10 carbon alkyl group, having 1 to 10 carbon atoms in the alkoxy group, having 5 to 10 of the cycloalkyl group, or C 6 being aryl Kii of to 10, R ¹ to R ³ of the 2 or more is a modified conjugated diene-based polymer having an alkoxy group having 1 to 10 carbon atoms. delete According to claim 1,
In Formula 2,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms including N, O and S atoms, or one hetero atom selected from the group consisting of N, O and S atoms, and R ¹¹ is In the case of O, or an S atom, R ¹² is absent,
R ¹² is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms, including to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a carbon number A monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a 4 to 10 heteroaryl group,
o and p are each independently 0, or an integer of 1 to 10, a modified conjugated diene-based polymer. delete According to claim 1,
In Formula 2,
A ^{modified conjugated diene-based polymer wherein R 12} is one substituent selected from the group consisting of functional groups represented by Formulas 4 to 12. According to claim 1,
In Formula 3,
R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 20 carbon atoms,
an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or one or more heteroatoms selected from the group consisting of N and Si substituted with one or more substituents selected from the group consisting of an alkylsilyl group monosubstituted, disubstituted, or trisubstituted with an alkyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms, including to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 3 to 10 carbon atoms, or a carbon number A modified conjugated diene-based polymer that is a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a 4 to 10 heteroaryl group. According to claim 1,
In Formula 3,
R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 20 carbon atoms, or a modified conjugated diene-based polymer that is a substituent selected from the group consisting of functional groups represented by Chemical Formulas 4 to 12. In a hydrocarbon solvent, in the presence of an organometallic compound, polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer to prepare an active polymer to which an organometal is bonded (S1);
preparing a first modified conjugated diene-based polymer by reacting the active polymer with a first modifier comprising a compound represented by Formula 1 or Formula 2 below (S2); and
A method for preparing a modified conjugated diene-based polymer comprising the step (S3) of reacting the first modified conjugated diene-based polymer with a second modifier comprising a compound represented by the following formula (3):
[Formula 1

In Formula 1,
R ¹ to R ³ are each independently an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and a cycloalkyl group having 5 to 30 carbon atoms. 6 to 30 aryl group, or a heteroaryl group having 4 to 30 carbon atoms, R ¹ to R ^{3 at} least 2 is necessarily an alkoxy group having 1 to 30 carbon atoms,
R ⁴ is one kind of substituent selected from the group consisting of functional groups represented by the following formulas 4 to 12,
[Formula 2]

In Formula 2,
R ⁵ to R ¹⁰ are each independently an alkoxy group having 1 to 30 carbon atoms, wherein ^{at least one substituent among the substituents of R 5} to R ¹⁰ is a functional group represented by the following Chemical Formula 11 or Chemical Formula 12,
R ¹¹ is an alkylene group having 1 to 10 carbon atoms, a heteroalkylene group having 1 to 10 carbon atoms including N, O and S atoms, or one hetero atom selected from the group consisting of N, O and S atoms, and R ¹¹ is In the case of O, or an S atom, R ¹² is absent,
R ¹² is an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms,
o and p are each independently 0, or an integer from 1 to 20,
[Formula 3]

In Formula 3,
R ¹³ to R ¹⁶ are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; Or at least one hetero selected from the group consisting of N, O, S and Si substituted with one or more substituents selected from the group consisting of a mono-, di-, or tri-substituted alkylsilyl group having 1 to 10 carbon atoms. A monovalent hydrocarbon group having 1 to 10 carbon atoms containing one or more atoms, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, Or a monovalent hydrocarbon group having 1 to 10 carbon atoms substituted with a heteroaryl group having 4 to 30 carbon atoms,
F ¹ to F ⁴ are each independently one kind of substituent selected from the group consisting of functional groups represented by the following Chemical Formulas 4 to 14,
n is an integer from 1 to 10,
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In Formulas 4 to 14,
* is a bonding position, TMS is a trimethylsilyl group, Et is an ethyl group, and R ¹⁷ to R ²⁰ are each independently an alkyl group having 1 to 30 carbon atoms. 10. The method of claim 9,
The organometallic compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium , n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium Alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and at least one selected from the group consisting of lithium isopropylamide, modified conjugated diene-based polymer production method . 10. The method of claim 9,
The polymerization of the step (S1) is a modified conjugated diene-based polymer manufacturing method that is carried out including a polar additive. 12. The method of claim 11,
The polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and a method for producing at least one modified conjugated diene-based polymer selected from the group consisting of tetramethylethylenediamine. 10. The method of claim 9,
The first modified conjugated diene-based polymer prepared in step (S2) includes a first modifier-derived functional group bonded to one end of the polymer, and the first modifier-derived functional group includes at least one alkoxy group having 1 to 30 carbon atoms. A method for producing a modified conjugated diene-based polymer comprising a. 10. The method of claim 9,
The reaction of step (S3) is a modified conjugated diene-based polymer production method that is carried out in a reactor, or a stripper (stripper). 10. The method of claim 9,
Prior to the step (S3), a method for producing a modified conjugated diene-based polymer comprising the step of pre-treating a second modifier. 16. The method of claim 15,
The step of pre-treating the second modifier is a method for producing a modified conjugated diene-based polymer comprising the step of stirring _{the second modifier and water (H 2 O).} A rubber composition comprising the modified conjugated diene-based polymer according to any one of claims 1, 2, 4, and 6 to 8 and a filler. 18. The method of claim 17,
The rubber composition is a rubber composition comprising 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.