KR102281110B1 - Modified diene polymer and preparation method thereof - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer comprising a functional group derived from a compound represented by Formula 1 and a method for preparing the same. Accordingly, the modified conjugated diene-based polymer includes a compound-derived functional group represented by Formula 1, such as a tertiary amine group, an ester group, an aliphatic hydrocarbon group, and an amide group, and thus may have excellent affinity with a filler such as silica, abrasion and processability This can be excellent.

Description

Modified conjugated diene-based polymer and method thereof {Modified diene polymer and preparation method thereof}

The present invention relates to a modified conjugated diene-based polymer comprising a functional group derived from a compound represented by Formula 1 and a method for preparing the same.

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

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

As a rubber material having a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of low wet skid resistance. Accordingly, recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been 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 rubber, 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 tires.

When such a solution-polymerized SBR is used as a rubber material for a tire, the glass transition temperature of the rubber can be increased by increasing the vinyl content in the SBR to control the required physical properties of the tire such as running resistance and braking force, and the glass transition temperature can be appropriately adjusted It can be adjusted to reduce fuel consumption.

Accordingly, as a method for increasing 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 that can interact with the filler has been proposed. . For example, a method of modifying the polymerization active terminal of a conjugated diene-based polymer with a tin-based compound, introducing an amine group, or modifying with an alkoxysilane derivative has been proposed.

For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the end of a polymer chain obtained by polymerization of styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is bound using a binder such as a tin compound. .

Meanwhile, 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 skid 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. You need 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.

Therefore, there is a need to develop a rubber having high affinity with fillers including silica.

US 4,397,994 A

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a modified conjugated diene-based polymer comprising a filler, particularly a silica-based filler affinity functional group.

Another 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, there is provided a modified conjugated diene-based polymer comprising a functional group derived from a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ² is a C 1 to C 20 divalent hydrocarbon group 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; or a divalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ³ and R ⁴ are each independently substituted or unsubstituted 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

n is an integer from 1 to 3.

In addition, the present invention prepares an active polymer having an alkali metal bonded to at least one terminal by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent (step (step) One); And it provides a method for producing a modified conjugated diene-based polymer according to claim 1 comprising the step (step 2) of reacting the active polymer with a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ² is a C 1 to C 20 divalent hydrocarbon group 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; or a divalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ³ and R ⁴ are each independently substituted or unsubstituted 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

n is an integer from 1 to 3.

The modified conjugated diene-based polymer according to the present invention includes a compound-derived functional group represented by Formula 1, for example, a tertiary amine group, an ester group, an aliphatic hydrocarbon group, and an amide group, so it can have excellent affinity with a filler such as silica, and abrasion resistance and excellent processability.

In addition, the production method according to the present invention can easily prepare a modified conjugated diene-based polymer having a high modification rate by performing a modification reaction using the compound represented by Formula 1 as a modifying agent.

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 present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The term "substitution" used in the present invention 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 plural substituents may be present depending on the number of hydrogens to be used. 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 and isopropyl, sec-butyl) , tert-butyl (tert-butyl) and neopentyl (neo-pentyl) may include all of the branched alkyl group.

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

In the present invention, the "cycloalkyl group" may mean including all of a cyclic saturated hydrocarbon, or a cyclic unsaturated hydrocarbon including one or two or more unsaturated bonds.

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 ( It may mean including all polycyclic aromatic hydrocarbons).

The terms “derived unit” and “derived functional group” used in the present invention may indicate a component, structure, or substance itself derived from a certain substance.

The term "monovalent hydrocarbon group" used in the present invention refers to a monovalent substituent derived from a hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, an aryl group, etc. may represent a monovalent atomic group in which carbon and hydrogen are bonded, 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, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, or a cyclo containing one or more unsaturated bonds. It may represent a divalent atomic group in which carbon and hydrogen are bonded, such as an alkylene group and an arylene group, 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 excellent affinity with a filler, particularly a silica-based filler.

The modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that it includes a functional group derived from a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ² is a C 1 to C 20 divalent hydrocarbon group 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; or a divalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O,

R ³ and R ⁴ are each independently substituted or unsubstituted 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

n is an integer from 1 to 3.

Specifically, in Formula 1, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O. can

When R ¹ is a monovalent hydrocarbon group ^{having 1 to 20 carbon atoms, R 1} is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. may be selected from the group consisting of, and specifically, R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms. may be selected.

In addition, if short of the R ¹ 1 is a hydrocarbon group having 1 to 20 carbon atoms which contains a hetero atom, wherein R ¹ comprises a heteroatom in place of one or more carbon atoms within the hydrocarbon group; Alternatively, one or more hydrogen atoms bonded to carbon atoms in the hydrocarbon group may be substituted with a hetero atom or a functional group containing a hetero atom, wherein the hetero atom may be selected from the group consisting of N, O and S. Specifically, if a monovalent hydrocarbon group having 1 to 20 carbon atoms in which the R ₁ include a hetero atom, and an alkoxy group; phenoxy group; carboxyl group; acid anhydride group; amine group; amide group; epoxy group; mercapto group; -[R ¹¹ O]xR ¹² ( ^{wherein R 11} is an alkylene group having 2 to 20 carbon atoms, R ¹² is a hydrogen atom, 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 an arylalkyl group having 7 to 20 carbon atoms, and x is an integer of 2 to 10); A monovalent hydrocarbon group having 1 to 20 carbon atoms including at least one functional group selected from the group consisting of a hydroxyl group, an alkoxy group, a phenoxy group, a carboxy group, an ester group, an acid anhydride group, an amine group, an amide group, an epoxy group, and a mercapto group For example, a hydroxyalkyl group, an alkoxyalkyl group, a phenoxyalkyl group, an aminoalkyl group, or a thiolalkyl group). More specifically, when R ¹ is an alkyl group having 1 to 20 carbon atoms including a hetero atom, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, a phenoxyalkyl group having 7 to 20 carbon atoms, 1 to carbon atoms 20 aminoalkyl group and -[R ¹¹ O]xR ¹² ( ^{wherein R 11} is an alkylene group having 2 to 10 carbon atoms, R ¹² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and 6 carbon atoms. It may be selected from the group consisting of an aryl group of to 18 and an arylalkyl group having 7 to 18 carbon atoms, and x is an integer of 2 to 10).

In addition, in Formula 1, R ² may be a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent hydrocarbon group having 1 to 20 carbon atoms including at least one hetero atom selected from the group consisting of N, S and O. .

When R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, R ₂ is an alkylene group having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, or a propylene group; an arylene group having 6 to 20 carbon atoms, such as a phenylene group; Or a combination group thereof may be an arylalkylene group having 7 to 20 carbon atoms. More specifically, R ² may be an alkylene group having 1 to 6 carbon atoms. In addition, R ₂ may be 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.

In addition, when R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including a hetero atom, R ² may include a hetero atom instead of one or more carbon atoms in the hydrocarbon group; Alternatively, one or more hydrogen atoms bonded to carbon atoms in the hydrocarbon group may be substituted with a hetero atom or a functional group containing a hetero atom, wherein the hetero atom may be selected from the group consisting of N, O and S.

Specifically, when R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms including a hetero atom, an alkoxy group; phenoxy group; carboxyl group; acid anhydride group; amine group; amide group; epoxy group; mercapto group; It may be a divalent hydrocarbon group having 1 to 20 carbon atoms including at least one functional group selected from the group consisting of a hydroxyl group, an alkoxy group, a phenoxy group, a carboxy group, an ester group, an acid anhydride group, an amine group, an amide group, an epoxy group, and a mercapto group. there is.

In addition, in Formula 1, R ³ and R ⁴ are each independently substituted or unsubstituted 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. It may be a cyclic monovalent hydrocarbon group, and more specifically, R ³ and R ⁴ are each independently 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 12 carbon atoms. It may be an alkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with one or more substituents.

In addition, in another embodiment of the present invention, in the compound of Formula 1, R ¹ is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. , is any one selected from the group consisting of an alkoxyalkyl group having 2 to 10 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms and an aminoalkyl group ^{having 1 to 10 carbon atoms, R 2} is an alkylene group having 1 to 10 carbon atoms, R ³ And R ⁴ may be each independently an alkyl group having 1 to 10 carbon atoms.

More specifically, the compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2 below.

[Formula 1-1]

[Formula 1-2]

The modified conjugated diene-based polymer according to the present invention may be prepared by the manufacturing method described later, 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 the modified structural units constituting the copolymer are disorderly arranged.

The modified conjugated diene-based polymer may include a tertiary amine group, an ester group, an aliphatic hydrocarbon group, an amide group, and an alkoxysilane group, which are functional groups derived from the compound represented by Formula 1. The tertiary amine group prevents aggregation between the fillers by interfering with hydrogen bonding between the hydroxyl groups present on the surface of the filler, thereby improving the dispersibility of the filler. In addition, the ester group and the aliphatic hydrocarbon group, in particular, the linear aliphatic hydrocarbon group may increase the affinity for the polymerization solvent to increase the solubility. In addition, the alkoxysilane group may be a functional group on the surface of the filler, for example, when the filler is silica, a condensation reaction with a silanol group on the surface of the silica to improve the abrasion resistance and processability of the polymer.

Therefore, the modified conjugated diene-based polymer according to an embodiment of the present invention may have excellent affinity with a filler, particularly silica, by including a functional group derived from the compound represented by Chemical Formula 1, and thus compounding properties with the filler The processability of the rubber composition including the modified conjugated diene-based polymer may be excellent, and as a result, the tensile strength, abrasion resistance and viscoelastic properties of a molded article manufactured using the rubber composition, such as a tire, may be improved. .

In addition, the modified conjugated diene-based polymer has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol], specifically 10,000 g/mol to 2,000,000 g/mol, more specifically 100,000 g/mol to 2,000,000 g/mol.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1.05 to 10.0. Specifically, the molecular weight distribution may be 1.1 to 4.0.

In addition, when the modified conjugated diene-based polymer according to an embodiment of the present invention is applied to a rubber composition, considering the good balance of mechanical properties, elastic modulus and processability of the rubber composition, the weight distribution range as described above is The average molecular weight and the number average molecular weight may be simultaneously satisfied in the above-mentioned range.

Specifically, the modified conjugated diene-based polymer may have a molecular weight distribution of 4.0 or less, a number average molecular weight of 10,000 g/mol to 2,000,000 g/mol, and more specifically, a molecular weight distribution of 4.0 or less, and a number average molecular weight It may be 100,000 g/mol to 2,000,000 g/mol.

Here, the weight average molecular weight and the number average molecular weight are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), respectively, and the molecular weight distribution (Mw/Mn) is also called polydispersity, and the weight average molecular weight (Mw) and It was calculated as a ratio (Mw/Mn) with a number average molecular weight (Mn).

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5 wt% or more, specifically 10 wt% or more, more specifically 15 wt% to 70 wt%, and when the vinyl content is in the above range, the glass transition temperature can be adjusted in an appropriate range, so that when applied to tires, the properties required for tires such as running resistance and braking power are excellent, and fuel consumption is reduced.

In this case, the vinyl content represents the content of the 1,2-added conjugated diene monomer, not the 1,4-added, based on 100 wt% of a 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 a high linearity of -S/R (stress/relaxation) value of 0.7 or more at 100 °C. In this case, the -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 rotational resistance when applied to the 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, and 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 that when applied to a rubber composition, resistance characteristics and fuel efficiency characteristics may be excellent. Specifically, the -S/R value of the modified conjugated diene-based polymer may be 0.7 to 1.0.

Here, the -S/R value was measured at 100° C. and a rotor speed of 2±0.02 rpm using a Mooney viscometer, for example, a Large Rotor of Monsanto MV2000E. Specifically, after leaving the polymer at room temperature (23±5℃) for more than 30 minutes, collecting 27±3g, filling it in the die cavity, and operating the platen to measure Mooney viscosity while applying torque, In addition, -S/R values were obtained by measuring the slope value of the Mooney viscosity change that appears as the torque is released for 1 minute.

In addition, the present invention provides a method for producing a modified conjugated diene-based polymer comprising a functional group derived from the compound represented by the formula (1).

The manufacturing method according to an embodiment of the present invention comprises polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent to bind an alkali metal to at least one terminal. preparing a polymer (step 1); and reacting the active polymer with a compound represented by the following formula (1) (step 2).

[Formula 1]

In Formula 1, R ¹ to R ⁴ are as defined above.

Step 1 is a step for preparing an active polymer in which an alkali metal derived from an organic alkali metal compound is bonded to at least one terminal, and a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of a polymerization initiator in a hydrocarbon solvent. It can be carried out by polymerization.

The conjugated diene-based monomer is not particularly limited, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl. It may be at least one 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 at least 60% by weight of the unit derived from the conjugated diene-based monomer in the finally prepared modified conjugated diene-based polymer, specifically 60% by weight or more and less than 100% by weight, more specifically 60% by weight to 85% by weight may be used in an amount included.

The aromatic vinyl-based monomer is not particularly limited, for example, 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 the conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the aromatic vinyl-based monomer contains 40 wt% or less of the aromatic vinyl-based monomer-derived unit in the finally prepared modified conjugated diene-based polymer, specifically It may be used in an amount comprised of 40 wt% or more and more than 0 wt%, more specifically 15 wt% to 40 wt%.

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.

The organic alkali metal compound may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.

The organic alkali metal compound is, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t- butyl lithium, hexyl lithium, n-decyl lithium, t- octyl lithium, phenyl lithium, 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. Specifically, the organic alkali metal compound may be n-butyllithium.

The polymerization of step 1 may be performed by further adding a polar additive as necessary, and the polar additive may be added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomer. Specifically, it may be added in an amount of 0.001 parts by weight to 1 parts by weight, more specifically 0.005 parts by weight to 0.1 parts by weight, based on 100 parts by weight of the total monomer.
In addition, the polymerization in Step 1 is performed by adding a polar additive, and the polar additive may be added in an amount of 0.001 g to 10 g based on 1 mmol of the total monomer.

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 tetramethylethylenediamine may be at least one selected from the group consisting of.

In the manufacturing method according to an embodiment of the present invention, when copolymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer by using the polar additive, a random copolymer can be easily formed by compensating for a difference in their reaction rate. can induce

In addition, the polymerization in step 1 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 adding an organic alkali metal compound, which is a polymerization initiator, and then polymerizing with the heat of its own reaction without optionally applying heat, and the elevated temperature polymerization is optionally heat after the polymerization initiator is added. It represents a polymerization method of increasing the temperature by adding , and the isothermal polymerization refers to a polymerization method in which heat is added to increase heat after the polymerization initiator is added, or heat is taken away to maintain a constant temperature of the polymer.

The polymerization may be carried out in a temperature range of -20 °C to 200 °C, specifically 20 °C to 150 °C, more specifically 10 °C to 120 °C for 15 minutes to 3 hours. can If it is carried out in the above temperature range, it is easy to control the polymerization reaction, and the polymerization reaction rate and efficiency can be excellent.

Step 2 is a step of reacting the active polymer with the compound represented by Formula 1 in order to prepare a modified conjugated diene-based polymer. In this case, step 2 may be a denaturation reaction step.

Specifically, the compound represented by Formula 1 may be used in a ratio of 0.1 to 10 moles relative to 1 mole of the organic alkali metal compound.

If the compound is used in an amount that falls within the above ratio range, it is possible to perform a denaturation reaction with optimal performance, thereby obtaining a conjugated diene-based polymer having a high denaturation rate.

The reaction of step 2 according to an embodiment of the present invention is a modification reaction for introducing a functional group into the polymer, and the reaction may be performed at a temperature of 10°C to 120°C for 10 minutes to 5 hours.

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

After completion of the above-described denaturation reaction, an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) or the like may be added to the polymerization reaction system to stop the polymerization reaction. Thereafter, the modified conjugated diene-based polymer may be obtained through desolvation treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through the supply of water vapor. In addition, an unmodified, active polymer may be included in the reaction product obtained as a result of the above-mentioned modification reaction together with the above-mentioned modified conjugated diene polymer.

The manufacturing method according to an embodiment of the present invention may further include one or more steps of recovering and drying the solvent and unreacted monomers as needed after step 2 above.

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

The rubber composition according to an embodiment of the present invention contains the modified conjugated diene-based polymer in an amount of 0.1 wt% or more and 100 wt% or less, specifically 10 wt% to 100 wt%, more specifically 20 wt% to 90 wt% may include. If the content of the modified conjugated diene-based polymer is less than 0.1 wt %, as a result, the improvement effect of abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, for example, a tire, etc. may be insignificant.

In addition, the rubber composition may further include other rubber components as necessary 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 an amount of 1 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, the rubber component may include natural rubber (NR) containing 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. may be synthetic rubbers, and any one or a mixture of two or more thereof may be used. there is.

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

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. When the nitrogen adsorption specific surface area of the carbon black ^{exceeds 250 m 2} /g, the processability of the rubber composition may decrease, and if it is ^{less than 20 m 2} /g, the reinforcing performance by the carbon black may be insignificant. In addition, if the DBP oil absorption amount of the carbon black exceeds 200 cc/100g, there is a fear that the processability of the rubber composition may decrease, and if it 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-silica having the most remarkable effect of improving fracture properties and coexistence of wet grip properties. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen surface area per gram, N ₂ SA) of 120 m / g to 180 m / g, and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 100 m / g to 200 m 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 the silica may decrease, and if it exceeds 180 m 2 /g, there is a fear that 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, the reinforcing performance by the silica filler may decrease, and if it exceeds 200 m / g, the processability of the rubber composition may decrease.

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

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-dimethylthiocarbamoyltetrasulfur 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 thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group having high affinity with a filler is introduced is used as a rubber component in the active site, the blending amount of the silane coupling agent is It can be reduced than the usual case. Specifically, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the filler. When used in the above range, it is possible to prevent gelation of the rubber component while sufficiently exhibiting the effect as a coupling agent. 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 according to the present invention may be crosslinkable with sulfur, and thus may further include a vulcanizing agent.

The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain low fuel economy.

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, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, an anti-scorch agent, zinc white ), stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The vulcanization accelerator is not particularly limited, and specifically, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), 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 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, in consideration of tensile strength and abrasion resistance, aromatic process oil price, hysteresis loss And in consideration of low-temperature characteristics, a naphthenic or paraffin-based process oil 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, and when included in the above content, it is possible to prevent deterioration of the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

In addition, the antioxidant is specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- oxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone; and the like. 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 kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the above formulation, and also 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

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

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

Preparation Example 1: Butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3-carboxylate (butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3 Preparation of -carboxylate) (i)

50.00 ml (206.34 mmol) of dibutyl itaconate and 150 ml of n-butanol were added to a 500 ml round-bottom flask, followed by stirring at room temperature and nitrogen conditions. After 10 minutes, 48.3 ml (206.34 mmol) of (3-amiropropyl)triethoxysilane was added, and the temperature was raised to 70° C. to react. During the reaction, the progress of the reaction was confirmed by thin layer chromatography (TLC) at each point in time, and after 24 hours of the reaction, the reaction was terminated and n-butanol was removed with an evaporator. Thereafter, the mixture was extracted 3 times with 100 ml of distilled water to remove the remaining n-butanol, and sodium sulfate was added to the organic layer, filtered and concentrated, followed by butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrroly. 71.58 g (yield: 93.3%) of din-3-carboxylate (i) was obtained. The nuclear magnetic resonance spectroscopy data ^{of 1} H of butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3-carboxylate (i) are as follows.

(i)

(i)

¹ H-NMR (500 MHz, CDCl ₃ ) δ 4.19-4.09(m, 2H), 3.81-3.77(q, 6H), 3.58-3.53(m, 2H), 3.25-3.23(t, 2H), 3.20- 3.15 (m, 1H), 2.71-2.59 (m, 2H), 1.63-1.57 (m, 4H), 1.39-1.32 (m, 2H), 1.27-1.18 (t, 9H), 0.93-0.89 (t, 3H) ), 0.58-0.54 (t, 2H).

Preparation Example 2: Methyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3-carboxylate (butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3 Preparation of -carboxylate) (ii)

In a 500 ml round-bottom flask, 25.0 ml (158.07 mmol) of dimethyl itaconate and 150 ml of methanol were added, followed by stirring at room temperature and nitrogen conditions. After 10 minutes, 37.0 ml (158.07 mmol) of (3-amiropropyl)triethoxysilane was added, and the temperature was raised to 70° C. to react. During the reaction, the reaction progress was confirmed by thin layer chromatography (TLC) at each point in time, and after 24 hours of reaction, the reaction was terminated and methanol was removed using an evaporator. Then, the mixture was extracted three times with 100 ml of distilled water to remove the remaining methanol, and sodium sulfate was added to the organic layer, filtered and concentrated, followed by methyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine- 56.40 g (yield: 94.0%) of 3-carboxylate (ii) was obtained. The nuclear magnetic resonance spectroscopy data ^{of 1} H of methyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3-carboxylate (i) are as follows.

(ii)

(ii)

¹ H-NMR (500 MHz, CDCl ₃ ) δ 3.83-3.79(q, 6H), 3.74(s, 3H), 3.60-3.56(m, 2H), 3.28-3.25(t, 2H), 3.24-3.21( m, 1H), 2.72-2.65 (m, 2H), 1.65-1.59 (m, 2H), 1.23-1.20 (t, 9H), 0.60-0.57 (t, 2H).

Example 1

In a 20 L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene, 5 kg of n-hexane, and 0.86 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, and the temperature inside the reactor was lowered to 40. The temperature was raised to °C. When the internal temperature of the reactor reached 40° C., 4 mmol of n-butyllithium was added to the reactor to conduct an adiabatic temperature rise reaction. After about 20 minutes, 20 g of 1,3-butadiene was added, and after 5 minutes, the butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3-carbohydrate prepared in Preparation Example 1 1.5 mmol of carboxylate (i) was added and reacted for 15 minutes. Then, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which the antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby preparing a modified styrene-butadiene copolymer.

Example 2

In Example 1, methyl 5-oxo-1 prepared in Preparation Example 2 instead of butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3-carboxylate (i) A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that -(3-(triethoxysilyl)propyl)pyrrolidine-3-carboxylate (ii) was added.

Comparative Example 1

In a 20 L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene, 5 kg of n-hexane, and 0.86 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, and the temperature inside the reactor was lowered to 40. The temperature was raised to °C. When the internal temperature of the reactor reached 40° C., 4 mmol of n-butyllithium was added to the reactor to conduct an adiabatic temperature rise reaction. After about 20 minutes, 20 g of 1,3-butadiene was added, and after 5 minutes, 1.4 mmol of dimethyldichlorosilane, a coupling agent, was added and reacted for 15 minutes. Then, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which the antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby preparing a modified styrene-butadiene copolymer.

Comparative Example 2

3,3'-((3-(trie) instead of butyl 5-oxo-1-(3-(triethoxysilyl)propyl)pyrrolidine-3-carboxylate (i) prepared in Preparation Example 1 Modified styrene-butadiene copolymer in the same manner as in Example 1, except that oxysilyl) propyl) azanediyl) dipropionate (3,3'-((3- (triethoxysilyl) propyl) azanediyl) dipropionate was used. was prepared.

Experimental Example 1

The physical properties of each of the modified styrene-butadiene polymers prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured in the following manner, and the results are shown in Table 1 below.

1) Styrene-derived unit and vinyl content

Styrene-derived units (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). In this case, as the column, two PLgel Olexis columns manufactured by Polymer Laboratories and one PLgel mixed-C column were used in combination. In addition, all of the newly replaced columns used a mixed bed type column, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

3) Mooney viscosity and -S/R value

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

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

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 denaturation denaturalization denaturalization denaturalization denaturalization NMR (wt%) Styrene-derived unit 36.3 36.4 36.3 36.3 vinyl content 29.7 29.3 29.4 29.5 GPC Results Mn (x10 ⁵ g/mol) 65.0 67.3 66.5 68.6 Mw (x10 ⁵ g/mol) 110.0 125.0 122.0 120.0 Mw/Mn 1.69 1.86 1.83 1.74 MV(ML1+4, @100℃) (MU) 109.7 110.9 106.8 109.2

Experimental Example 2

After preparing a rubber composition and a rubber specimen using each of the modified styrene-butadiene copolymers prepared in Examples 1 and 2 and Comparative Examples 1 and 2, tensile properties and viscoelastic properties were respectively measured as follows. The results are shown in Table 2 below.

Specifically, the rubber composition was prepared through a first-stage kneading process and a second-stage kneading process for each rubber composition. In this case, the amount of the material other than the modified styrene-butadiene copolymer is shown based on 100 parts by weight of the modified styrene-butadiene copolymer. In the first stage kneading, 137.5 parts by weight of each of the modified styrene-butadiene 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, 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid, 2 parts by weight of antioxidant, and 1 part by weight of wax were mixed and kneaded. At this time, the temperature of the kneader was controlled and a primary formulation was obtained at a discharge temperature of 145°C 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 (0°C to 70°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 running resistance (fuel efficiency).

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Tensile properties Tensile strength (kgf/cm ² ) 213 209 205 226 300% tensile stress (kgf/cm ² ) 114 114 120 123 Viscoelastic properties Tan δ at 0℃ 0.891 0.882 0.837 0.853 Tan δ at 60 0.099 0.099 0.107 0.102

As shown in Table 2, the rubber specimens prepared using the modified styrene-butadiene copolymers of Examples 1 and 2 according to an embodiment of the present invention used the modified styrene-butadiene copolymers of Comparative Examples 1 and 2 It was confirmed that the viscoelastic properties were improved while exhibiting a similar level of tensile properties compared to the prepared rubber specimens.

Claims (13)

A modified conjugated diene-based polymer comprising a functional group derived from a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ is an alkyl group having 1 to 20 carbon atoms,
R ² is an alkylene group having 1 to 10 carbon atoms,
R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms,
n is an integer from 1 to 3.
delete delete delete The method according to claim 1,
The compound represented by Formula 1 is a modified conjugated diene-based polymer that is a compound represented by Formula 1-1 or Formula 1-2:
[Formula 1-1]

[Formula 1-2]

The method according to claim 1,
The modified conjugated diene-based polymer is 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 according to claim 1,
The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 1,000 g / mol to 2,000,000 g / mol.
The method according to claim 1,
The polymer is a modified conjugated diene-based polymer having a molecular weight distribution (Mw/Mn) of 1.05 to 10.
1) preparing an active polymer having an alkali metal bonded to at least one terminal by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent; and
2) A method for producing the modified conjugated diene-based polymer according to claim 1, comprising the step of reacting the active polymer with a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ is an alkyl group having 1 to 20 carbon atoms,
R ² is an alkylene group having 1 to 10 carbon atoms,
R ³ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms,
n is an integer from 1 to 3.
10. 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-tolylithium, 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 of the modified conjugated diene-based polymer manufacturing method.
10. The method of claim 9,
The method for producing a modified conjugated diene-based polymer wherein the organic alkali metal compound is used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.
10. The method of claim 9,
The polymerization of step 1) is performed by adding a polar additive,
The polar additive is a method for producing a modified conjugated diene-based polymer is added in an amount of 0.001 g to 10 g based on 1 mmol of the total monomer.
10. The method of claim 9,
The method for producing a modified conjugated diene-based polymer wherein the compound represented by Formula 1 is used in a ratio of 0.1 to 10 moles relative to 1 mole of the organic alkali metal compound.