KR20160065016A - Modified styrene-butadiene copolymer, preparation method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified styrene-butadiene copolymer with a high modification rate including a modifier-derived functional group represented by below Chemical formula 1, a method of preparing the same, a rubber composition including the same, and a tire produced from the rubber composition. In chemical formula 1, A, R1 to R5, m and n are as defined in the specification.

Description

MODIFIED STYRENE-BUTADIENE COPOLYMER, METHOD FOR PREPARING THE SAME, AND RUBBER COMPOSITION CONTAINING THE SAME Technical Field The present invention relates to a modified styrene-butadiene copolymer, a preparation method thereof and a rubber composition comprising the same,

The present invention relates to a high-modulus modified styrene-butadiene copolymer, a process for producing the same, a rubber composition containing the same, and a tire made from the rubber composition.

In recent years, as a rubber material for a tire, a conjugated diene polymer having low rolling resistance, excellent abrasion resistance, tensile properties, and adjustment stability typified by a wet skid resistance has been required in recent years in response to demand for low fuel consumption in automobiles.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As the evaluation index of such vulcanized rubber, repulsive elasticity of 50 DEG C to 80 DEG C, tan delta, Goodrich heat, and the like are used. That is, a rubber material having a large rebound resilience at that temperature or a small tan δ or Goodrich heat is preferable.

Natural rubbers, polyisoprene rubbers, polybutadiene rubbers, and the like are known as rubber materials having a small hysteresis loss, but these have a problem of low wet skid resistance. Recently, a conjugated diene (co) polymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) is prepared by emulsion polymerization or solution polymerization and is used as a rubber for a tire . Of these, the greatest advantage of solution polymerization over emulsion polymerization is that vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled and molecular weight and physical properties, etc., can be controlled by coupling, It can be adjusted. Therefore, it is possible to easily change the structure of the finally prepared SBR or BR rubber, to reduce the movement of chain ends due to bonding or modification of chain ends, and to increase the bonding force with fillers such as silica or carbon black, It is widely used as 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 is increased by increasing the vinyl content in the SBR, so that the tire required properties such as running resistance and braking force can be controlled, Adjustment can reduce fuel consumption.

The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and chain ends of the formed polymer are bonded or denatured by using various modifiers.

On the other hand, carbon black, silica and the like are used as reinforcing fillers for tire treads. When silica is used as a reinforcing filler, low hysteresis loss property and wet skid resistance are improved. However, silica having a hydrophilic surface compared to carbon black on the hydrophobic surface has a disadvantage that the affinity with the rubber is low and the dispersibility is poor. Therefore, in order to improve the dispersibility or to provide the bond between the silica and the rubber, It is necessary to use a lingering agent.

Accordingly, a method of introducing a functional group having affinity or reactivity with silica into the end portion of the rubber molecule has been attempted, but the effect is insufficient.

Further, when only the affinity to silica is improved, the affinity with carbon black relatively decreases, and the application range may be limited.

Therefore, it is necessary to develop a rubber having high affinity with not only silica but also carbon black.

KR 2013-0090811 A JP 2013-082842A

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art, and it is an object of the present invention to provide a high stiffness modified styrene-butadiene copolymer.

Another object of the present invention is to provide a process for producing the modified styrene-butadiene copolymer.

It is still another object of the present invention to provide a rubber composition comprising the above modified styrene-butadiene copolymer.

It is still another object of the present invention to provide a tire produced using the rubber composition.

Still another object of the present invention is to provide a modifier useful in the production of the modified styrene-butadiene copolymer.

In order to solve the above problems, the present invention provides a modified styrene-butadiene copolymer containing a functional group derived from a modifier represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of N, S and O,

R ¹ and R ² are each independently substituted with one or more substituents selected from the group consisting of a linear or branched 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, A divalent hydrocarbon group having 1 to 20 carbon atoms,

R ³ to R ⁵ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,

m is an integer of 0 to 3, and n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.

The present invention also provides a process for producing an active polymer to which an alkali metal is bonded by polymerizing an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organometallic compound in a hydrocarbon solvent (step 1); And reacting the active polymer with a modifier represented by the formula (1) (step 2).

The present invention also provides a rubber composition comprising the modified styrene-butadiene copolymer.

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

Further, the present invention provides a modifier having the structure of the above formula (1).

The modified styrene-butadiene copolymer according to the present invention may have excellent affinity with a filler such as silica by including a modifier-derived functional group represented by the general formula (1) such as a tertiary amine group and a silica-affinitive group or a hexane- It can exhibit a high modification rate.

Also, the modified styrene-butadiene copolymer according to the present invention can easily produce a modified styrene-butadiene copolymer having a high degree of modification by the high solubility of the modifier by using the modifier represented by the formula (1).

In addition, the rubber composition according to the present invention may have excellent processability by including a modified styrene-butadiene copolymer having excellent affinity with a filler. As a result, a work product (for example, a tire) Strength, abrasion resistance, and wet road surface resistance characteristics.

In addition, the modifier represented by formula (1) according to the present invention has an effect of preventing the increase of the pattern viscosity due to the hydrolysis and condensation reaction by introducing a carbonyl group having high reactivity at the anion end.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
Fig. 1 schematically shows a denaturation reaction using a denaturant according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a modified styrene-butadiene copolymer having excellent affinity with a filler and improved processability.

The modified styrene-butadiene copolymer according to an embodiment of the present invention is characterized by including a modifier-derived functional group represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of N, S and O,

R ¹ and R ² are each independently substituted with one or more substituents selected from the group consisting of a linear or branched 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, A divalent hydrocarbon group having 1 to 20 carbon atoms,

R ³ to R ⁵ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,

m is an integer from 0 to 3, and

n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.

The modified styrene-butadiene copolymer may be prepared by reacting an active polymer having an organic alkali metal bonded thereto and a modifier represented by the formula (1) through a production method described later, wherein the modified styrene- The physical properties can be improved by including the modifier-derived functional group represented by the formula

The modifier represented by the above-mentioned formula (1) is a functional group capable of improving the physical properties of the copolymer and contains at least one of a functional group for improving the inorganic filler dispersibility and an inorganic filler affinity functional group and a solvent affinity functional group .

Specifically, the modifier of the above formula (1) includes an ester group exhibiting a high reactivity with respect to the active site of the active polymer, whereby the styrene-butadiene copolymer can be modified with a high modification ratio. As a result, -Butadiene copolymer in a high yield. The modifier may be one containing an amino group, specifically a tertiary amino group, as a functional group capable of improving the dispersibility of the inorganic filler by preventing aggregation of the inorganic filler in the rubber composition. For example, when silica is used as the inorganic filler, aggregation tends to occur due to hydrogen bonding between hydroxyl groups present on the surface. On the other hand, the tertiary amino group in the modifier interferes with the hydrogen bonding between the hydroxyl groups, so that the dispersibility of the silica can be improved. In addition, the modifier may be added to the inorganic filler-affinity functional group capable of improving abrasion resistance and processability of the rubber composition by interaction with the inorganic filler together with the amino group, And a solvent-affinity functional group that exhibits chemical conversion. The inorganic filler-affinity functional group is specifically an alkoxysilyl group, which is introduced into a styrene-butadiene copolymer, and then a functional group on the surface of the inorganic filler, for example, a condensation reaction with a silanol group on the surface of silica when the inorganic filler is silica, -Butadiene copolymer of the present invention can be improved. Such an improvement can be improved as the number of alkoxysilyl groups increases. In addition, the solvent affinity functional group is specifically a hydrocarbon group such as an alkyl group or an aryl group, and increases the solubility of the modifier in the solvent during the modification process for the styrene-butadiene copolymer. As a result, the modification ratio of the styrene- Can be improved.

Specifically, in Formula 1, A may be a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of N, S, and O.

When A is a hydrocarbon group of 1 to 20 carbon atoms, it is selected from the group consisting of 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 More specifically, A may be selected from the group consisting of 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 have.

When A is a hydrocarbon group having 1 to 20 carbon atoms including a hetero atom, it may contain a hetero atom in place of at least one carbon atom in the hydrocarbon group; Or one or more hydrogen atoms bonded to a carbon atom within a hydrocarbon group may be replaced by a heteroatom or a heteroatom-containing functional group, wherein the heteroatom may be selected from the group consisting of N, O and S. More specifically, when A is a hydrocarbon group having 1 to 20 carbon atoms including a hetero atom, an alkoxy group; Phenoxy group; A carboxy group; Acid anhydride groups; An amino group; Amide group; An epoxy group; A mercapto group; - [R ¹¹ O] _x R ¹² wherein R ¹¹ is an alkylene group having 2 to 20 carbon atoms and 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 hydrocarbon group having 1 to 20 carbon atoms containing at least one functional group selected from the group consisting of a hydroxyl group, an alkoxy group, a phenoxy group, a carboxyl group, an ester group, an acid anhydride group, an amino group, an amide group, A hydroxyalkyl group, an alkoxyalkyl group, a phenoxyalkyl group, an aminoalkyl group or a thiolalkyl group). More specifically, when A is an alkyl group having 1 to 20 carbon atoms containing a hetero atom, the alkoxy group having 1 to 20 carbon atoms, the alkoxyalkyl group having 2 to 20 carbon atoms, the phenoxyalkyl group having 7 to 20 carbon atoms, R ¹¹ O] _x R ¹² wherein R ¹¹ is an alkylene group having 2 to 10 carbon atoms and R 12 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a carbon number of 6 An aryl group having 6 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms, and x is an integer of 2 to 10).

In Formula 1, R ¹ and R ² are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, specifically, 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 and the like; Or an arylalkylene group having 7 to 20 carbon atoms as a combinator thereof. More specifically, R ¹ and R ² may each independently be an alkylene group having 1 to 5 carbon atoms. More specifically, R ¹ is an alkylene group having 2 or 3 carbon atoms, and R ² is an alkylene group having 1 to 3 carbon atoms. Each of R ¹ and R ² is independently selected from the group consisting of a linear or branched 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 is possible.

Each of R ³ to R ⁵ is independently a monovalent hydrocarbon group of 1 to 20 carbon atoms, specifically, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 6 to 18 carbon atoms An aryl group, and a combination thereof. More specifically, R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, and R ⁵ may be an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms. More specifically, R ³ to R ⁵ may each independently be an alkyl group having 1 to 5 carbon atoms.

In Formula 1, m is an integer of 0 to 3, more specifically, an integer of 0 to 2. And n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.

More specifically, in the formula (1), A represents 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, an arylalkyl group having 7 to 12 carbon atoms, an alkoxy group having 2 to 10 carbon atoms An alkyl group, a phenoxyalkyl group having 7 to 12 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, and - [R ¹¹ O] _x R ¹² Wherein R ¹¹ is an alkylene group having 2 to 10 carbon atoms and R ¹² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms And x is an integer of 2 to 10), R ¹ and R ² are each independently an alkylene group having 1 or 5 carbon atoms, and R ³ and R ⁴ are each independently selected from the group consisting of R ⁵ is an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, m is an integer of 0 to 2 and n is an integer of 1 or 2, N is an integer of 2 when the alkyl group has 1 to 20 carbon atoms, the cycloalkyl group has 3 to 20 carbon atoms, the aryl group has 6 to 20 carbon atoms, or the arylalkyl group has 7 to 20 carbon atoms.

More specifically, the modifier is selected from the group consisting of 2-methoxyethyl 3- (bis (3-triethoxysilylpropyl) amino) propanoate, 2-phenoxyethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate), 2-methoxyethyl 3- 2-methoxyethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate), 2- Ethoxyethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate, ethyl (2-ethoxyethyl) Propylamino) propanoate, ethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate, 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate (2-phenoxyethyl 3- (cyclohexyl 2-methoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, which is a 2-methoxyethyl 3- (cyclohexyl ), 2- (dimethylamino) ethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, 2,5-dimethylaminoethyl 3- , 8,11,14,17,20,23,26-nonaoxaoctanoic acid-28-yl 3- (bis (3-triethoxysilyl) propyl) amino) propanoate 2- (2- (2- (2-phenoxyethoxy) ethyl) amino) propanoate, Ethoxy) ethoxy) ethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate (3- (triethoxysilyl) propyl) amino) propanoate, 2- (dimethylamino) ethyl 3- ( bis (3- (triethoxys propyl) amino) propanoate), 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (bis (3- (cyclohexyl (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (cyclohexyl (triethoxysilyl) methyl) amino) propanoate), 2-methoxyethyl 3- Propylamino) propanoate) or ethyl 3- (bis (3- (diethylamino) propyl) amino) Propyl) amino) propanoate), and any one or a mixture of two or more of them may be used. The term " ethyl (3- (diethylamino) Can be used.

Among these, the modifier of the above formula (1) is preferably 2-phenoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, 2-methoxyethyl 3- (cyclohexyl ) Methyl) amino) propanoate, 2- (dimethylamino) ethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, 2,5,8,11,14,17,20, 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate, 2- (2- (2- (2- phenoxyethoxy) Ethoxy) ethoxy) ethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate, 2-phenoxyethyl 3- (3-triethoxysilyl) propanoate, 2- (dimethylamino) ethyl 3- (bis (3-triethoxysilyl) propyl) Amino) propanoate, 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (3-bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate and ethyl 3- (bis 3- (diethoxy (methyl) silyl) propyl) amino) propanoate.

Further, the modifier may have a solubility of 10 g or more in a non-polar solvent such as 100 g of hexane at 25 ° C and 1 atm. Here, the solubility of a denaturant means a degree of dissolution that is clear without a cloudy phenomenon when observed with the naked eye. By exhibiting such high solubility, it is possible to exhibit an excellent modification ratio with respect to the styrene-butadiene copolymer.

The modifier according to the present invention has an optimized functional group capable of maximizing the affinity with an inorganic filler and a solvent, so that it can be used as a modifier of a styrene-butadiene copolymer so that the styrene-butadiene copolymer has excellent viscoelasticity, It is possible to impart processability.

On the other hand, the modified styrene-butadiene copolymer may be a copolymer of a conjugated diene monomer and an aromatic vinyl monomer. That is, the modified styrene-butadiene copolymer may include a conjugated diene monomer-derived unit and an aromatic vinyl monomer-derived unit.

The term " derived unit " in the present invention may refer to an ingredient, structure, or the substance itself resulting from a substance.

The modified styrene-butadiene copolymer may be a random copolymer.

In the present invention, the term " random copolymer " may indicate that the constituent units constituting the copolymer are randomly arranged.

Examples of the conjugated diene monomer include, but are not limited to, 1,3-butadiene, 2,3-dimenyl-1,3-butadiene, piperylene, 3- Phenyl-1,3-butadiene, and the like.

The modified styrene-butadiene copolymer may contain 60% by weight or more, specifically 60% by weight to 90% by weight, more specifically 60% by weight to 85% by weight, of units derived from a conjugated diene monomer.

Examples of the aromatic vinyl monomer include, but not limited to, styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- -Methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.

The modified styrene-butadiene copolymer may contain 40% by weight or less, specifically 10% by weight to 40% by weight, more specifically 15% by weight to 40% by weight, of units derived from an aromatic vinyl monomer.

The modified styrene-butadiene copolymer has a number average molecular weight 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 Lt; / RTI >

The modified styrene-butadiene copolymer may have a molecular weight distribution (Mw / Mn) of 1.1 to 10, specifically 1.1 to 5, more specifically 1.1 to 4. When the modified styrene-butadiene copolymer has the molecular weight distribution as described above, the processability of the rubber composition containing the modified styrene-butadiene copolymer is improved, and as a result, the mechanical properties, fuel consumption characteristics and wear resistance of the produced molded article can be improved.

The modified styrene-butadiene copolymer may have a vinyl content of 5 wt%, specifically 10 wt% or more, and more specifically 14 wt% to 70 wt%. If the modified styrene-butadiene copolymer shows the vinyl content in the above range, the glass transition temperature can be adjusted to an appropriate range, so that it is possible to satisfy physical properties required for a tire such as running resistance and braking force But it has the effect of reducing fuel consumption.

Here, the vinyl content means the content of the 1,2-added conjugated diene monomer, not 1,4-added to 100% by weight of the styrene-butadiene copolymer composed of the vinyl group-containing monomer and the aromatic vinyl-based monomer .

The present invention also provides a process for producing a modified styrene-butadiene copolymer comprising a modifier-derived group represented by the above formula (1).

According to an embodiment of the present invention, there is provided a method for producing an active polymer, comprising: polymerizing an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organometallic compound in a hydrocarbon solvent to prepare an active polymer having an alkali metal bonded thereto (Step 1); And reacting the active polymer with a modifier represented by the following formula (1) (step 2).

[Chemical Formula 1]

In Formula 1,

A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of N, S and O,

R ¹ and R ² are each independently substituted with one or more substituents selected from the group consisting of a linear or branched 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, A divalent hydrocarbon group having 1 to 20 carbon atoms,

R ³ to R ⁵ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,

m is an integer of 0 to 3, and n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.

Step 1 is a step for preparing an active polymer having an organometallic bond, and may be carried out by polymerizing a conjugated diene monomer and an aromatic vinyl monomer in the presence of an organometallic compound in a hydrocarbon solvent.

The active polymer may be a polymer in which a polymer anion and an organometallic cation are bonded.

The specific types of the conjugated diene-based monomer and the aromatic vinyl-based monomer may be as described above, and the amount of each monomer used is such that the units derived from the conjugated dienic monomer in the modified styrene-butadiene copolymer and the units derived from the aromatic vinyl- Or the like.

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

The organometallic compound may be one or more selected from the group consisting of an organic alkali metal compound or an organic lithium compound, an organic sodium compound, an organic potassium compound, an organic rubidium compound, and an organic cesium compound.

Specifically, the organometallic compound is at least one compound selected from the group consisting of methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, N-octyl lithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, At least one selected from the group consisting of potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropyl amide.

The organometallic compound may be used in an amount of 0.01 to 10 mmol based on 100 g of the monomer. Specifically, the organometallic compound may be used in an amount of 0.05 mmol to 5 mmol, more specifically 0.1 mmol to 2 mmol, more specifically 0.1 mmol to 1 mmol, based on 100 g of the monomer.

The polymerization of the step 1 may be carried out by adding a polar additive if necessary, and the polar additive is added in an amount of 0.001 to 50 g, specifically 0.001 to 10 g, more specifically 0.001 to 10 g, May be added in an amount of 0.005 g to 0.1 g.

The polar additive may be added in an amount of 0.001 to 10 g, specifically 0.005 to 1 g, more specifically 0.005 to 0.1 g, based on 1 mmol of the organometallic compound.

The polar additive may be a salt, an ether, an amine or a mixture thereof. Specific examples of the polar additive include tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloalcohol ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, di (Meth) acrylates are preferred from the group consisting of ethylene glycol, dimethyl ether, tertiary butoxyethoxyethane bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine It may be more than one kind selected. More specifically, it may be ditetrahydropropyl propane, triethylamine or tetramethylethylenediamine.

In the production method according to an embodiment of the present invention, when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive, the random copolymer can be easily formed .

The polymerization in the step 1 may be anionic polymerization, specifically, a living anionic polymerization in which an active site is obtained by a growth reaction with an anion.

The polymerization may be temperature-raising polymerization, isothermal polymerization or constant temperature polymerization (adiabatic polymerization).

Here, the constant-temperature polymerization is a polymerization method comprising a step of polymerizing an organometallic compound in a self-reaction heat without any heat, and after the introduction of the organometallic compound, heat is applied arbitrarily to the temperature And the isothermal polymerization is a polymerization method in which the organometallic compound is added and then heat is applied to increase the heat or heat to keep the temperature of the polymer constant.

The polymerization may be carried out in a temperature range of -20 캜 to 200 캜, specifically, in a temperature range of 0 캜 to 150 캜, more specifically, 10 캜 to 120 캜.

Step 2 is a step of reacting the active polymer with the modifier represented by the formula (1) to prepare a modified styrene-butadiene copolymer.

The modifier represented by the above formula (1) may be the same as described above, or one or more of them may be mixed and used in the reaction.

The modifier represented by Formula 1 may be used in an amount of 0.1 mol to 10 mol based on 1 mol of the organometallic compound. Specifically, the modifier represented by the formula (1) may be used in an amount of 0.3 mol to 2 mol based on 1 mol of the organometallic compound. If the modifier is used in an amount in the range of the above range, the modifying reaction with the optimum performance can be performed, and a styrene-butadiene copolymer having a high modifying ratio can be obtained.

The reaction of step 2 may be a modification reaction for introducing a functional group into the copolymer, and the reaction may be carried out at 0 캜 to 90 캜 for 1 minute to 5 hours.

The modified styrene-butadiene copolymer according to an embodiment of the present invention may be produced by a batch polymerization method or a continuous polymerization method including at least one type of reactor.

The manufacturing method according to an embodiment of the present invention may further include at least one step of recovering and drying the solvent and unreacted monomers after the step 2, if necessary.

The present invention also provides a rubber composition comprising the modified styrene-butadiene copolymer.

The rubber composition according to an embodiment of the present invention comprises 10% by weight or more, specifically 10% by weight to 100% by weight, more specifically 20% by weight to 90% by weight, of a modified styrene-butadiene copolymer . If the content of the modified styrene-butadiene copolymer is less than 10% by weight, the effect of improving the abrasion resistance and crack resistance of a molded article produced using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components in addition to the modified styrene-butadiene copolymer, if necessary, and the rubber component may be contained in an amount of 90 wt% or less based on the total weight of the rubber composition. Specifically, the modified styrene-butadiene copolymer may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified styrene-butadiene copolymer.

The rubber component may be natural rubber or synthetic rubber, for example natural rubber (NR) comprising 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 with the general natural rubber; Butadiene copolymers (SBR), polybutadiene (BR), polyisoprenes (IR), butyl rubbers (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, neoprene, poly Butadiene), poly (styrene-co-butadiene), poly (styrene-co-butadiene) Synthetic rubber such as polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber and the like, and any one or a mixture of two or more thereof may be used have.

In addition, the rubber composition may contain 0.1 to 200 parts by weight of the filler per 100 parts by weight of the modified styrene-butadiene copolymer. Specifically, the rubber composition may include 10 to 120 parts by weight of the filler.

The filler may be a silica-based filler. The silica-based filler is not particularly limited, but may be, for example, wet silica (hydrated silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. More specifically, the filler may be a wet silica having the most remarkable effect of improving the fracture characteristics and the wet grip.

In addition, the rubber composition according to an embodiment of the present invention may further include a carbon black-based filler, if necessary.

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

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzyltetrasulfide, 3-triethoxysilylpropylmethacrylate Monosulfide, monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl- N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. Any one or a mixture of two or more of them may be used. More specifically, in consideration of the reinforcing effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazine tetrasulfide.

In the rubber composition according to the embodiment of the present invention, since a modified polymer having a functional group with high affinity for silica is introduced into the active site as a rubber component, the amount of the silane coupling agent to be added is usually Can be reduced. Specifically, the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight based on 100 parts by weight of silica. When used in the above-mentioned range, gelation of the rubber component can be prevented while sufficiently exhibiting the effect as a coupling agent. More specifically, the silane coupling agent may be used in an amount of 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur-crosslinkable, and may further include a vulcanizing agent.

The vulcanizing agent may be specifically a sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When contained in the above content range, the required elastic modulus and strength of the vulcanized rubber composition can be ensured, and at the same time, the low fuel consumption ratio can be obtained.

In addition to the above-mentioned components, the rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, antioxidants, scorch inhibitors, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is not particularly limited and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can 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.

The process oil may be a paraffinic, naphthenic or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, the process oil may be an aromatic process oil, a hysteresis loss And naphthenic or paraffinic process oils may be used in view of the low temperature characteristics. The process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. When the content is included in the above amount, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber can be prevented from lowering.

Specific examples of the antioxidant include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- 2, 4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone. The antioxidant may be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to one embodiment of the present invention can be obtained by kneading by using a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.

Accordingly, the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, Can be useful for the production of various industrial rubber products.

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

The tire may be a tire or a tire tread.

Further, the present invention provides a denaturant useful for denaturing the modified styrene-butadiene copolymer.

The above-mentioned modifier is as described above.

Meanwhile, the modifier represented by Formula 1 according to an embodiment of the present invention may be prepared by reacting a compound of Formula 2 with a compound of Formula 3 below.

(2)

(3)

In formulas (2) and (3), A, R ² to R ⁵ , m and n are as defined above,

R is an alkyl group having 2 to 20 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of a linear or branched 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 Lt; / RTI >

More specifically, in Formula 2, R may be an alkenyl group having 2 to 10 carbon atoms, and more specifically, an alkenyl group having 2 to 5 carbon atoms such as an ethylene group.

More specifically, the compound of Formula 2 may be ethylene glycol methyl ether acrylate, 2-phenoxyethyl acrylate, ethylacrylate, or the like. The compound of the above formula (3) may be prepared by reacting bis [3- (triethoxysilyl) propyl] amine or bis (methyldiethoxysilylpropyl) amine ) And the like.

The compounds of formulas (2) and (3) may be used in stoichiometric amounts. Specifically, the compound of formula (3) may be used in an amount of 0.01 to 0.2 molar ratio relative to 1 mol of the compound of formula (2) 0.1, more specifically from 0.05 to 0.08 molar ratio.

The reaction of the compound of Formula 2 and the compound of Formula 3 may be carried out in an aqueous solvent. Examples of the aqueous solvent include alcohols (for example, lower alcohols having 1 to 5 carbon atoms such as ethanol and the like), and any one or a mixture of two or more thereof may be used.

The reaction of the compound of Formula 2 and the compound of Formula 3 may be carried out under an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.

The reaction of the compound of Formula 2 with the compound of Formula 3 may be carried out at a temperature ranging from 20 ° C to 60 ° C. If the temperature is lower than 20 ° C during the reaction, the reaction rate may become too slow and the reaction efficiency may be lowered. If the temperature exceeds 60 ° C during the reaction, the reaction rate becomes too fast to control the reaction.

By such a production method as described above, it is possible to easily produce a modifier which simultaneously contains a single intramolecular filler affinity functional group and a solvent affinity functional group.

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

Manufacturing example 1: 2 - Phenoxyethyl  3- ( Cyclohexyl ((triethoxysilyl) methyl) amino ) Propanoate  Produce

5.744 mmol of (N-cyclohexylaminomethyl) triethoxysilane (Gelest) was dissolved in 5 ml of ethanol and dissolved in 50 ml of a round bottom flask. To the solution was added 5.744 mmol of 2-phenoxyethyl acrylate (TCI) Lt; / RTI > for 8 hours under nitrogen. After completion of the reaction, the solvent was distilled off under reduced pressure, followed by distillation under reduced pressure at 120 ° C to obtain 4.990 mmol of 2-phenoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate compound of the following formula (i) (Yield: 91.4%). Nuclear magnetic resonance spectroscopic data of ¹ H of purified 2-phenoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate is as follows.

(i)

(i)

^{1 H-NMR (500 MHz,} CDCl 3) δ 7.49-7.23 (m, 2H), δ 6.97-6.86 (m, 3H), δ 4.40-4.36 (m, 2H), δ 4.16-34.03 (m, 4H) (m, 3H),? 3.87-3.81 (m, 3H),? 2.78-2.75 (m, 2H),? 2.50-2.41 , [delta] 1.26-1.16 (m, 12H)

Manufacturing example 2: 2 - Methoxyethyl  3- ( Cyclohexyl ((triethoxysilyl) methyl) amino ) Propanoate  Produce

8.468 mmol of (N-cyclohexylaminomethyl) triethoxysilane (Gelest) was dissolved in 5 ml of ethanol, and 8.468 mmol of ethylene glycol methyl ether acrylate (Acros) was added to a 50 ml round bottom flask And the mixture was stirred at room temperature under nitrogen for 8 hours. After the completion of the reaction, the solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure at 120 ° C to obtain 8.19 mmol of 2-methoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate of the following formula (ii) (Yield: 96.7%). Nuclear magnetic resonance spectroscopic data of ¹ H of purified 2-methoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate are as follows.

(ii)

(ii)

^{1 H-NMR (500 MHz,} CDCl 3) δ 4.18-4.16 (t, 2H), δ 3.84-3.79 (m, 3H), δ3.55-3.54 (t, 2H), δ 3.35 (s, 3H), (m, 3H),? 1.73-1.71 (m, 7H),? 1.22-1.18 (m, 13H)

Manufacturing example 3: 2 - (dimethylamino) ethyl 3- ( Cyclohexyl ((triethoxysilyl) methyl) amino ) ≪ / RTI > propanoate

6.586 mmol of (N-cyclohexylaminomethyl) triethoxysilane (Gelest) was added to 5 ml of ethanol and dissolved in a 50 ml round-bottomed flask, and then 6.586 mmol of 2- (dimethylamino) ethyl acrylate (Sigma-Aldrich) And the mixture was stirred at room temperature under a nitrogen atmosphere for 8 hours. After the completion of the reaction, the solvent was removed under reduced pressure, and the mixture was distilled under reduced pressure at 120 ° C to obtain 2- (dimethylamino) ethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate compound 6 (Yield: 94.8%). Nuclear magnetic resonance spectroscopic data of ¹ H of purified 2- (dimethylamino) ethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate are as follows.

(iii)

(iii)

^{1 H-NMR (500 MHz,} CDCl 3) δ 4.16-4.08 (m, 3H), δ 2.76-2.73 (m, 2H), δ2.53-2.50 (m, 3H), δ 2.47-2.41 (m, 3H ),? 2.25-2.23 (m, 10H),? 2.11-2.08 (t, 2H),? 1.73-1.72 (m, 9H),? 1.54-1.47 (m, 4H),? 1.24-1.16 )

Manufacturing example 4: 2 , 5,8,11,14,17,20,23,26- Nona japan -28-yl 3- ( Bis (3- (triethoxysilyl) propyl) amino ) ≪ / RTI > propanoate

(Ethylene glycol) methyl ether acrylate (Sigma-Aldrich) was added to 2.279 mmol of bis (3-triethoxysilylpropyl) amine (2.279 mmol) in a 50 ml round bottom flask and dissolved in 5 ml of ethanol. Mn 480), and the mixture was stirred at room temperature under nitrogen for 8 hours. After completion of the reaction, the solvent was removed by decompression, and the mixture was distilled under reduced pressure at 120 ° C to obtain 2,5,8,11,14,17,20,23,26-nonanooxaoctanoic acid-28-yl 3 - (bis (3- (triethoxysilyl) propyl) amino) propanoate compound (yield: 93.5%). A solution of purified 2,5,8,11,14,17,20,23,26-nonaoxaoctanoic acid-28-yl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate The nuclear magnetic resonance spectroscopic data of ¹ H are as follows.

(iv)

(iv)

^{1 H-NMR (500 MHz,} CDCl 3) δ 4.17-4.15 (t, 2H), δ 3.78-3.73 (m, 12H), δ 3.60-3.59 (m, 32H), δ 3.50-3.48 (m, 2H) (m, 2H),? 3.32 (s, 3H),? 2.74-2.71 (m, 2H),? 2.37-2.34 (t, 6H),? 1.50-1.43 (m, 4H),? 1.19-1.15 0.54-0.50 (m, 4H)

Manufacturing example 5: 2 - (2- (2- (2- Phenoxyethoxy ) Ethoxy ) Ethoxy ) Ethyl 3- ( Bis (3- (triethoxysilyl) propyl) amino ) ≪ / RTI > propanoate

2.279 mmol of bis (3-triethoxysilylpropyl) amine and 5 ml of ethanol were added to a 50-ml round-bottomed flask to dissolve and then 2.279 mmol of poly (ethylene glycol) phenyl ether acrylate (Sigma-Aldrich, Mn 324) And the mixture was stirred at room temperature under a nitrogen atmosphere for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, followed by distillation under reduced pressure at 120 ° C to obtain 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (bis (Triethoxysilyl) propyl) amino) propanoate compound (yield: 93.7%). The ¹ H nucleus of the purified 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate The magnetic resonance spectroscopic data are as follows.

(v)

(v)

^{1 H-NMR (500 MHz,} CDCl 3) δ 7.26-7.22 (t, 2H), δ 6.92-6.87 (m, 3H), δ4.20-4.17 (t, 2H), δ 4.11-4.07 (m, 3H ), 3.84-3.82 (m, 2H),? 3.81-3.75 (m, 10H),? 3.71-3.60 (m, 10H),? 2.77-2.74 (t, 2H),? 2.39-2.36 ),? 1.52-1.46 (m, 4H),? 1.21-1.78 (m, 18H),? 0.57-0.53 (m, 4H)

Manufacturing example 6: 2 - Phenoxyethyl  3- ( Bis (3- (triethoxysilyl) propyl) amino ) Propanoate  Produce

4.57 mmol of bis (3-triethoxysilylpropyl) amine (Gelest) and 5 ml of ethanol were added to a 50-ml round-bottomed flask and dissolved. To the solution was then added 557 mmol of 2-phenoxyethyl acrylate (TCI) And the mixture was stirred at room temperature under nitrogen for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, followed by distillation under reduced pressure at 120 占 폚 to obtain 4.17 mmol (yield) of 2-phenoxyethyl 3- (bis (3- (triethoxysilyl) propyl) amino) (Yield: 91.6%). Nuclear magnetic resonance spectroscopic data of ¹ H of purified 2-phenoxyethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate is as follows.

(vi)

(vi)

^{1 H-NMR (500 MHz,} CDCl 3) δ 7.26-7.23 (m, 2H), δ 6.94-6.84 (m, 3H), δ4.39-4.37 (t, 2H), δ 4.14-4.12 (t, 3H ),? 3.79-3.75 (m, 12H),? 2.78-2.75 (t, 2H),? 2.46-2.43 (t, 2H),? 2.39-2.36 (t, 4H),? 1.63-1.43 ),? 1.20-1.17 (m, 18H),? 0.56-0. 52 (m, 4H)

Manufacturing example 7: 2 - Methoxyethyl  3- ( Bis (3- (triethoxysilyl) propyl) amino ) Propanoate  Produce

4.557 mmol of bis (3-triethoxysilylpropyl) amine (Gelest) and 5 ml of ethanol were added to a 50 ml round-bottomed flask and dissolved. 4.557 mmol of ethylene glycol methyl ether acrylate (Acros) Lt; / RTI > for 8 hours under nitrogen. After completion of the reaction, the solvent was distilled off under reduced pressure, followed by distillation under reduced pressure at 120 占 폚 to obtain 4.430 mmol of 2-methoxyethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate of the following formula (Yield: 97.3%). Nuclear magnetic resonance spectroscopic data of ¹ H of purified 2-methoxyethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate is as follows.

(vii)

(vii)

^{1 H-NMR (500 MHz,} CDCl 3) δ 4.21-4.19 (t, 2H), δ 3.81-3.77 (m, 12H), δ 3.57-3.56 (t, 2H), δ 3.36 (s, 3H), δ (T, 2H), 2.47-2.46 (t, 2H), 2.79-2.76 (t, 2H) 0.57-0.54 (t, 4H)

Manufacturing example 8: 2 - (dimethylamino) ethyl 3- ( Bis (3- (triethoxysilyl) propyl) amino ) ≪ / RTI > propanoate

4.5573 mmol of bis (3-triethoxysilylpropyl) amine (Gelest) and 5 ml of ethanol were added to and dissolved in a 50 ml round-bottom flask, and then 4.55764 mmol of 2- (dimethylamino) ethyl acrylate (Sigma-Aldrich) And further stirred at room temperature under nitrogen for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, followed by distillation under reduced pressure at 120 占 폚 to obtain 2- (dimethylamino) ethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate 4.18 mmol (yield: 91.7%). Nuclear magnetic resonance spectroscopic data of ¹ H of the purified 2- (dimethylamino) ethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate are as follows.

(viii)

(viii)

^{1 H-NMR (500 MHz,} CDCl 3) δ 4.12-4.09 (t, 2H), δ 3.78-3.74 (m, 12H), δ 2.75-2.73 (t, 2H), δ 2.51-2.49 (t, 3H) (m, 6H),? 1.54-1.44 (m, 4H),? 1.18-1.15 (m, 18H) , [delta] 0.52-0. 50 (m, 4H)

Manufacturing example 9: 2 - (2- (2- (2- Phenoxyethoxy ) Ethoxy ) Ethoxy ) Ethyl 3- ( Cyclohexyl ((triethoxysilyl) methyl) amino ) ≪ / RTI > propanoate

(Ethyleneglycol) phenyl ether acrylate (Sigma-Aldrich, Mn 324) 3.449 (N-cyclohexylaminomethyl) triethoxysilane was dissolved in 50 ml of a round- mmol, and the mixture was stirred at room temperature under nitrogen for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was distilled under reduced pressure at 120 ° C to obtain 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (cyclohexyl ((Triethoxysilyl) methyl) amino) propanoate compound (yield: 91.1%). The ¹ H nuclear magnetic domain of purified 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate The resonance spectroscopic data are as follows.

(ix)

(ix)

^{1 H-NMR (500 MHz,} CDCl 3) δ 7.26-7.24 (m, 2H), δ 6.93-6.88 (m, 3H), δ 4.18-4.16 (m, 2H), δ 4.11-4.09 (m, 3H) (m, 2H),? 2.50-2.39 (m, 3H),? 2.10-2.09 (m, 2H) , 1.74-1.72 (m, 4H),? 1.58-1.59 (m, 1H)? 1.24-1.15

Manufacturing example 10: 2 - Methoxyethyl  3- ( Bis (3- (diethoxy (methyl) silyl) propyl) amino ) Propanoate  Produce

73.03 mmol of bis (methyldiethoxysilylpropyl) amine (Gelest) was dissolved in 20 mL of ethanol and dissolved in 73.03 mmol of ethylene glycol methyl ether acrylate (Acros), and the mixture was poured into a 100 mL round- Lt; / RTI > for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, followed by distillation under reduced pressure at 120 ° C to obtain 2-methoxyethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate compound 71.77 mmol (yield: 98.327%). Nuclear magnetic resonance spectroscopic data of ¹ H of purified 2-methoxyethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate are as follows.

(x)

(x)

^{1 H-NMR (500 MHz,} CDCl 3) δ 4.23-4.21 (t, 2H), δ 3.78-3.74 (m, 8H), δ3.60-3.58 (t, 2H), δ 3.39 (s, 3H), (t, 2H),? 2.81-2.78 (t, 2H),? 2.49-2.46 (t, 2H),? 2.42-2.39 [delta] 0.57-0.54 (t, 4H), [delta] 0.12 (s, 6H)

Manufacturing example  11: Ethyl 3- ( Bis (3- (diethoxy (methyl) silyl) propyl) amino ) Propanoate  Produce

72.99 mmol of bis (methyldiethoxysilylpropyl) amine (Gelest) and 20 ml of ethanol were added to a 100 ml round-bottomed flask, and 72.99 mmol of ethyl acrylate (Sigma-Aldrich) was added thereto. Lt; / RTI > After completion of the reaction, the solvent was removed by decompression, and the mixture was distilled under reduced pressure at 80 ° C to obtain 72.18 mmol of ethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate compound of the following formula (xi) (Yield: 98.9%). Nuclear magnetic resonance spectroscopic data of 1H of purified ethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate is as follows.

(xi)

(xi)

^{1 H-NMR (500 MHz,} CDCl 3) δ 4.14-4.10 (m, 2H), δ 3.78-3.74 (m, 8H), δ 2.80-2.79 (t, 2H), δ 2.43-2.39 (m, 6H) , 1.53-1.54 (m, 4H),? 1.27-1.20 (m, 15H),? 0.58-0.54 (t, 4H)

Example  1: Modified styrene-butadiene copolymer

29.7 g of styrene, 78.1 g of 1,3-butadiene, 550 g of n-hexane and 0.124 g of DTP (2,2-di (2-tetrahydrofuryl) propane) as a polar additive were introduced into a 2 L autoclave reactor, And the temperature was raised to 50 占 폚. When the internal temperature of the reactor reached 50 캜, 3 mmol of n-butyllithium was charged into the reactor to conduct an adiabatic reaction. After 20 minutes, 2.2 g of 1,3-butadiene was added to cap the SSBR terminal with butadiene. After 5 minutes, 0.181 g of the modifier 2-methoxyethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate prepared in Preparation Example 7 was added and the mixture was reacted for 15 minutes ([DTP] / [ act. Li] = 2.3, [denaturant] / [act. Li] = 1.0). Thereafter, the polymerization reaction was stopped using ethanol, and 4.5 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent. The solvent was then removed by roll drying to remove the remaining solvent and water, thereby preparing a modified conjugated diene-based copolymer.

Example  2

270 g of styrene, 710 g of 1,3-butadiene, 5 kg of n-hexane and 0.94 g of DTP (2,2-di (2-tetrahydrofuryl) propane) as a polar additive were placed in a 20 L autoclave reactor, The temperature was raised to 40 占 폚. When the internal temperature of the reactor reached 40 ° C, 25.40 g (2.62 wt% in hexane, 33% activation) of n-butyllithium was charged into the reactor to proceed with the adiabatic reaction. After 20 minutes, 20.0 g of 1,3-butadiene was added and the end of the SSBR was capped with butadiene. After 5 minutes, 1.98 g of the modifier ethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate was added thereto and reacted for 15 minutes ([DTP] / [act. Li] = 1.46, [modifier] / [act.Li] = 0.85). Thereafter, the polymerization reaction was stopped using ethanol, and 33 g of a solution in which 30 wt% of Wingstay K, an antioxidant, was dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent. The solvent was then removed by roll drying to remove the remaining solvent and water, thereby preparing a modified conjugated diene-based copolymer.

Comparative Example

A modified conjugated diene-based copolymer was prepared in the same manner as in Example 1, except that N, N-bis (triethoxysilylpropyl) piperazine was used as a modifier.

Experimental Example 1

(Mw), a number average molecular weight (Mn), a molecular weight distribution (MWD), a maximum peak molecular weight (Mp) and a number average molecular weight (Mw) of each of the modified conjugate dienic copolymers prepared in Examples 1, And the bonding efficiency (%) and the pattern viscosity (MV) were measured. The results are shown in Table 1 below.

The weight average molecular weight (Mw), number average molecular weight (Mn) and maximum peak molecular weight (Mp) were measured by GPC (Gel Permeation Chromatohraph) analysis. Molecular weight distribution (MWD, Mw / Was calculated from the measured molecular weights. Specifically, the GPC was a combination of two columns of PLgel Olexis (Polymer Laboratories) columns and a column of PLgel mixed-C (Polymer Laboratories). All of the new columns were of mixed bed type, The GPC reference material (polystyrene) was used for molecular weight calculation.

division GPC Mn (g / mol, X 10 ⁴ ) Mw (g / mol, X10 ⁴ ) Mp (g / mol, X 10 ⁴⁾ Coupling efficiency (%) Molecular weight distribution (Mw / Mn) Example 1 49 120 35 38 2.4 77 28 124 34 Example 2 27 42 30 40 1.4 64 60 Comparative Example 34 45 25 43 1.3 53 57

As shown in Table 1, the modified styrene-butadiene copolymers of Example 1 and Example 2 produced using the modifier according to the present invention are superior to the modified styrene-butadiene copolymers of the comparative example prepared using conventional modifiers, It was confirmed that the binding efficiency of the components remarkably increased.

Specifically, the modified styrene-butadiene copolymer of Example 1 and the modified styrene-butadiene copolymer of Comparative Example were compared with each other. As a result, the binding efficiency (62%, Mp 77 × 10 ⁴⁾ of the polymer component of the modified styrene- And 124 × 10 ⁴ ) was 2.7 times higher than the binding efficiency (57%, Mp 53 × 10 ⁴ ) of the polymer component of the styrene-butadiene copolymer of the comparative example.

The fact that the number of triethoxysilanes of the modifier is the same but the molecular weight is increased means that the modifier according to the present invention has an increased reactivity by introducing an ester group having high reactivity with the polymer active moiety, Respectively. In addition, it was confirmed that the coupling efficiency of the polymer component (60%) was increased with the high modification efficiency even though the amount of the modifier used in Example 2 was 77% of the amount of the modifier used in the comparative example. As shown in FIG. 1, the active site (-Li ⁺ ) of the metal-bonded copolymer is bound to oxygen in the ethylene glycol group of the modifier, and the reactivity of the anion increases, The modification reaction can be more easily achieved and the binding efficiency of the polymer component increases as described above.

Claims (26)

1. A modified styrene-butadiene copolymer comprising a functional group derived from a modifier represented by the following formula
[Chemical Formula 1]

In Formula 1,
A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of N, S and O,
R ¹ and R ² are each independently substituted with one or more substituents selected from the group consisting of a linear or branched 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, A divalent hydrocarbon group having 1 to 20 carbon atoms,
R ³ to R ⁵ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,
m is an integer of 0 to 3, and n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.
The method according to claim 1,
In Formula 1,
A is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, 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, an aminoalkyl group having 1 to 20 carbon atoms and - [R ¹¹ O] _x R ¹² wherein R ¹¹ is an alkylene group having 2 to 10 carbon atoms and R ¹² is a hydrogen atom, An alkyl group, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms, and x is an integer of 2 to 10). -Butadiene copolymer.
The method according to claim 1,
In Formula 1,
A 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, an arylalkyl group having 7 to 12 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, An aminoalkyl group having 1 to 10 carbon atoms and - [R ¹¹ O] _x R ¹² wherein R ¹¹ is an alkylene group having 2 to 10 carbon atoms and R ¹² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms An alkyl group having 6 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms, and x is an integer of 2 to 10)
R ¹ and R ² are each independently an alkylene group having 1 to 5 carbon atoms,
R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms,
R ⁵ is an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms,
m is an integer of 0 to 2, and n is an integer of 1 or 2, provided that A 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, Lt; / RTI > is an arylalkyl group of 1 to 20 carbon atoms, n is an integer of 2.
The method according to claim 1,
A is any one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a phenoxyalkyl group having 7 to 12 carbon atoms,
R ¹ and R ² are each independently an alkylene group having 1 to 5 carbon atoms,
R ³ and R ⁴ are each independently an alkyl group having 1 to 5 carbon atoms, and
m is an integer of 0 or 1, and n is an integer of 2.
The method according to claim 1,
The modifier may be selected from the group consisting of 2-phenoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, 2-methoxyethyl 3- (cyclohexyl (Cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, 2,5,8,11,14,17,20,23,26-nonaoxy 2- (2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) -2,3-dihydroxypropanoate, (3-triethoxysilyl) propyl) amino) propanoate, 2-phenoxyethyl 3- (bis (3-triethoxysilyl) propylamino) propanoate, 2- (dimethylamino) ethyl 3- (bis (3-triethoxysilyl) propyl) amino) propanoate, 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) ethyl 3- (cyclohexyl ((triethoxysilyl) ) Amino) propanoate, 2-methoxyethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate and ethyl 3- (bis ) Propyl) amino) propanoate. ≪ / RTI >
The method according to claim 1,
Wherein the copolymer comprises 1% by weight to 60% by weight of an aromatic vinyl-based monomer-derived unit.
The method according to claim 1,
Wherein the copolymer has a number average molecular weight of from 1,000 g / mol to 2,000,000 g / mol.
The method according to claim 1,
Wherein the copolymer has a molecular weight distribution (Mw / Mn) of 1.05 to 10.
The method according to claim 1,
Wherein the copolymer has a vinyl content of 5 wt% or more.
1) polymerizing an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organometallic compound in a hydrocarbon solvent to prepare an alkali-bonded active polymer; And
2) A process for producing the modified styrene-butadiene copolymer according to claim 1, which comprises reacting the active polymer with a modifier represented by the following formula
[Chemical Formula 1]

In Formula 1,
A is a hydrocarbon group of 1 to 20 carbon atoms or a hydrocarbon group of 1 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of N, S and O,
R ¹ and R ² are each independently substituted with one or more substituents selected from the group consisting of a linear or branched 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, A divalent hydrocarbon group having 1 to 20 carbon atoms,
R ³ to R ⁵ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,
m is an integer of 0 to 3, and n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.
The method of claim 10,
Wherein the organometallic compound is used in an amount of 0.01 to 10 mmol based on 100 g of the total of monomers.
The method of claim 10,
The organometallic compound is preferably selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t- cyclohexyl lithium, 3,5-di-n-heptyl cyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide Wherein the modified styrene-butadiene copolymer is at least one selected from the group consisting of sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide. Way.
The method of claim 10,
Wherein the polymerization of step 1) is carried out by further adding a polar additive.
14. The method of claim 13,
Wherein the polar additive is used in an amount of 0.001 g to 10 g based on 1 mmol of the organometallic compound.
The method of claim 10,
The modifier represented by the above-mentioned formula (1) can be obtained by a method in which the modifier is selected from the group consisting of 2-phenoxyethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, 2-methoxyethyl 3- Amino) propanoate, 2- (dimethylamino) ethyl 3- (cyclohexyl ((triethoxysilyl) methyl) amino) propanoate, 2,5,8,11,14,17, 2- (2- (2- (2-phenoxyphenyl) amino) propanoate, 2- (2- Ethoxy) ethoxy) ethyl 3- (bis (3- (triethoxysilyl) propyl) amino) propanoate, 2-phenoxyethyl 3- (3-triethoxysilyl) propanoate, 2- (dimethylamino) ethyl 3- (bis (3-triethoxysilyl) Propylamino) propanoate, 2- (2- (2- (2-phenoxyethoxy) ethoxy) ethoxy) Methoxyethyl 3- (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate and ethyl 3 (methoxycarbonyl) - (bis (3- (diethoxy (methyl) silyl) propyl) amino) propanoate.
The method of claim 10,
Wherein the modifier represented by Formula 1 is used in an amount of 0.1 mol to 10 mol based on 1 mol of the organometallic compound.
A rubber composition comprising the modified styrene-butadiene copolymer of claim 1.
18. The method of claim 17,
Wherein the rubber composition comprises at least 10% by weight of a modified styrene-butadiene copolymer.
18. The method of claim 17,
Wherein the rubber composition comprises 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the polymer.
The method of claim 19,
Wherein the filler is a silica-based filler, a carbon black-based filler, or a combination thereof.
A tire produced from the rubber composition of claim 17.
A modifier having a structure of the following formula (1):
[Chemical Formula 1]

In Formula 1,
A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of N, S and O,
R ¹ and R ² are each independently substituted with one or more substituents selected from the group consisting of a linear or branched 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, A divalent hydrocarbon group having 1 to 20 carbon atoms,
R ³ to R ⁵ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,
m is an integer of 0 to 3, and n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.
23. The method of claim 22,
Wherein A is any one selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 1 to 20 carbon atoms, and a phenoxyalkyl group having 7 to 20 carbon atoms,
R ¹ and R ² are each independently an alkylene group having 1 to 5 carbon atoms,
R ³ to R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms,
m is an integer of 0 or 1, and n is an integer of 2.
23. The method of claim 22,
Wherein the modifier is for modifying a styrene-butadiene copolymer.
A process for producing a denaturant according to claim 22, which comprises reacting a compound represented by the following formula (2) and a compound represented by the following formula (3)
(2)

(3)

In the above Formulas 2 and 3,
A is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms and containing at least one heteroatom selected from the group consisting of N, S and O,
R is an alkyl group having 2 to 20 carbon atoms, which is substituted or unsubstituted with at least one substituent selected from the group consisting of a linear or branched 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 Lt; / RTI >
R ² is a linear or branched 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, which is unsubstituted or substituted with one or more substituents selected from the group consisting of A divalent hydrocarbon group,
R ³ to R ⁵ are each independently a monovalent hydrocarbon group of 1 to 20 carbon atoms,
m is an integer of 0 to 3, and n is an integer of 1 or 2, provided that when A is a hydrocarbon group of 1 to 20 carbon atoms, n is an integer of 2.
26. The method of claim 25,
Wherein the compound of Formula 3 is used in a molar ratio of 0.01 to 0.2 based on 1 mole of the compound of Formula 2. [

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