KR20210036016A - Block copolymer, preparing method thereof and asphalt composition comprising the same - Google Patents

Abstract

The present invention relates to a block copolymer which has excellent compatibility with asphalt and is applied as an asphalt modifier, a method for preparing the same, and an asphalt composition comprising the same. The block copolymer provided herein comprises: a main chain unit comprising an aromatic vinyl hydrocarbon block composed of repeating units derived from aromatic vinyl hydrocarbons and a conjugated diene block composed of repeating units derived from a conjugated diene monomer; and a functional group derived from a polymerization terminator.

Description

Block copolymer, its manufacturing method, and asphalt composition comprising the same {BLOCK COPOLYMER, PREPARING METHOD THEREOF AND ASPHALT COMPOSITION COMPRISING THE SAME}

The present invention relates to a block copolymer having excellent compatibility with asphalt applied as an asphalt modifier, a method for producing the same, and an asphalt composition comprising the same.

Asphalt is a residue after most of the volatile oils evaporate among petroleum components, and maintains a highly viscous liquid or semi-solid state at high temperatures, but hardens at temperatures below room temperature.

Asphalt is widely used in building materials such as road pavement and waterproofing because it has rich plasticity, high waterproof, electrical insulation, and adhesive properties, and chemically stable. However, when exposed to high temperatures for a long period of time during use, plastic deformation occurs, and at low temperatures, there is a problem that cracks are generated due to external impact. In order to improve this problem, research has been conducted to improve the physical properties of the asphalt composition by adding various polymers.

For example, aromatic vinyl hydrocarbon-conjugated diene block copolymers such as styrene-butadiene-styrene (SBS) block copolymers are widely used as modifiers for improving the physical properties of asphalt compositions.

When using an aromatic vinyl hydrocarbon-conjugated diene block copolymer as an asphalt modifier, it takes a lot of time and cost for dissolution at high temperature, and thus, the most important property of the block copolymer used as an asphalt modifier is compatibility with an asphalt composition.

In addition, among the characteristics of asphalt, solubility and softening point are largely influenced by the characteristics of the modifier, and therefore, the development of a modifier with improved characteristics for shortening the dissolution time of asphalt and increasing the softening point is continuously progressing.

However, since the softening point and the solubility are in a trade-off relationship, there is a limit to increasing the softening point and improving the solubility at the same time.

KR 2016-0052310 A (2016.05.12.)

The present invention was devised to solve the problem of the technology behind the present invention, and it is applied as a modifier of asphalt to provide a block copolymer capable of improving the solubility and softening point, which is a trade-off relationship, because it has excellent compatibility with asphalt. It aims to do.

In addition, an object of the present invention is to provide a method for producing the block copolymer.

In addition, an object of the present invention is to provide an asphalt composition comprising the block copolymer and asphalt.

According to an embodiment of the present invention for solving the above problems, the present invention is a main chain comprising an aromatic vinyl hydrocarbon block consisting of repeating units derived from aromatic vinyl hydrocarbons and a conjugated diene block consisting of repeating units derived from conjugated diene monomers unit; And a functional group derived from a polymerization terminator, wherein the polymerization terminator is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1, 2, and 3:

[Formula 1]

[Formula 2]

[Formula 3]

.

.

In addition, the present invention comprises the steps of preparing an aromatic vinyl hydrocarbon block by polymerizing an aromatic vinyl hydrocarbon in the presence of a polymerization initiator in a hydrocarbon solvent (S1); Polymerizing the aromatic vinyl hydrocarbon block and the conjugated diene monomer to prepare a main chain unit including the aromatic vinyl hydrocarbon block and the conjugated diene block (S2); Coupling the main chain unit and a coupling agent (S3); And mixing with a polymerization terminating agent (S4), wherein the polymerization terminating agent is at least one selected from the group consisting of compounds represented by Formula 1, Formula 2, and Formula 3 below. to provide:

[Formula 1]

[Formula 2]

[Formula 3]

.

.

In addition, the present invention provides an asphalt composition comprising the block copolymer and asphalt.

The block copolymer according to the present invention has excellent compatibility with asphalt by including a functional group derived from a polymerization terminator at least at one end, and is applied as an asphalt modifier to improve the solubility and softening point of asphalt at the same time.

In addition, the method for preparing the block copolymer according to the present invention includes the step of terminating polymerization by mixing with a synthetic terminator having a functional group after the coupling reaction, thereby producing a block copolymer having excellent compatibility with asphalt.

In addition, the asphalt composition according to the present invention has excellent solubility and softening point by including the block copolymer as a modifier.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

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

In the present invention, the term'monomer-derived repeating unit' may refer to a component, structure, or substance itself derived from a monomer, and when the polymer is polymerized, the introduced monomer participates in the polymerization reaction and refers to a unit formed in the polymer. Can be.

In the present invention, the term'main chain unit' may refer to a block copolymer chain formed by polymerization of monomers.

The present invention is applied as a modifier for asphalt to provide a block copolymer capable of improving the solubility and softening point of asphalt.

The block copolymer according to an embodiment of the present invention includes a main chain unit including an aromatic vinyl hydrocarbon block consisting of repeating units derived from aromatic vinyl hydrocarbons and a conjugated diene block consisting of repeating units derived from conjugated diene monomers; And a functional group derived from a polymerization terminator, wherein the polymerization terminator is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1, 2, and 3.

[Formula 1]

[Formula 2]

[Formula 3]

.

.

In general, asphalt contains a component called asphaltene, a highly concentrated aromatic hydrocarbon compound with polar functional groups with heteroatoms. On the other hand, the aromatic vinyl hydrocarbon-conjugated diene block copolymer applied as an asphalt modifier does not have a polar functional group, and thus has low compatibility with asphalt, and as a result, the workability and workability of the asphalt composition are deteriorated. There is a problem in that the quality of asphalt such as elasticity deterioration is caused because it is not sufficiently mixed with asphalt. However, the block copolymer according to the present invention is prepared by the manufacturing method described below, and is compatible with asphalt by bonding a functional group derived from the polymerization terminator to a main chain unit including an aromatic vinyl hydrocarbon block and a conjugated diene block. This may be excellent, and it is applied as an asphalt modifier to improve the solubility and softening point of asphalt to improve workability and workability, thereby improving the quality of asphalt.

Hereinafter, the block copolymer according to the present invention will be described in more detail.

The block copolymer includes a block copolymer chain, which is a main chain unit formed by an aromatic vinyl hydrocarbon block formed by polymerization of an aromatic vinyl hydrocarbon and a conjugated diene block formed by polymerization of a conjugated diene monomer, and is bonded to the block copolymer chain. It may include a functional group derived from the polymerization terminator.

Here, the polymerization terminator-derived functional group may be bonded to at least one end of the main chain unit, and thus, compatibility with asphalt may be excellent.

The polymerization terminator may be one or more selected from the group consisting of compounds represented by Formula 1, Formula 2, and Formula 3 as described above, and improve compatibility with asphalt by introducing a polar functional group into the main chain unit. I can make it.

In addition, the polymerization terminating agent may be a compound represented by Chemical Formula 1 or Chemical Formula 3, and the compound represented by Chemical Formula 1 or Chemical Formula 3 contains a sulfur atom together with a polar functional group, so that it has more compatibility with asphalt. Can be improved.

Specifically, the polymerization terminator may react with a main chain unit having an anionic end after a coupling reaction by a manufacturing method described below to introduce a functional group such as a polar functional group into the block copolymer, whereby the block copolymer is polarized. When applied as an asphalt modifier, it has excellent compatibility with asphalt and can effectively improve the physical properties of asphalt.

In addition, the block copolymer may include 0.01 to 10 parts by weight of a polymerization terminator-derived functional group based on 100 parts by weight of the total weight of the main chain unit, and specifically, 0.1 to 3 parts by weight of a polymerization terminator-derived functional group. It can be, and within this range, the compatibility with asphalt can be more easily excellent.

In addition, the aromatic vinyl hydrocarbon block is composed of repeating units derived from aromatic vinyl hydrocarbons formed by polymerization of aromatic vinyl hydrocarbons, and the aromatic vinyl hydrocarbon includes 6 to 6 carbon atoms containing vinyl such as styrene, vinyl naphthalene, vinyl toluene or vinyl xylene. It may be an aromatic hydrocarbon-based compound of 30, and specifically, the aromatic vinyl hydrocarbon is a (alkyl) styrene having 1 to 20 carbon atoms, (cycloalkyl) styrene having 1 to 20 carbon atoms, aryl styrene having 6 to 30 carbon atoms, and 7 to 30 carbon atoms. Of aralkyl styrene, and more specifically, the aromatic vinyl styrene is styrene, alpha-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-(para-methylphenyl ) It may be one or more selected from the group consisting of styrene.

The aromatic vinyl hydrocarbon block may have a weight average molecular weight of 3,000 to 35,000 g/mol, or 10,000 to 25,000 g/mol, and within this range, it is possible to improve low-temperature physical properties while maintaining high-temperature physical properties and storage stability of asphalt.

In addition, the conjugated diene block is composed of repeating units derived from conjugated diene formed by polymerization of a conjugated diene monomer, and the conjugated diene monomer is a diolefin having a pair of conjugated double bonds, specifically 1,3-butadiene, It may be one or more selected from the group consisting of isoprene, 2,3-dimenyl-1,3-butadiene, and 2-phenyl-1,3-butadiene.

The conjugated diene block may have a weight average molecular weight of 10,000 to 150,000 g/mol, or 20,000 to 100,000 g/mol, and within this range, the block copolymer may have excellent mechanical melt properties and excellent processability.

In another example, the block copolymer may have a weight ratio of an aromatic vinyl hydrocarbon block and a conjugated diene block of 1:1 to 1:4, and is applied as an asphalt modifier within this range to be stably dissolved in an asphalt composition and sufficient asphalt. It can express a modifying effect.

As another example, the block copolymer may be represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

A to C are each independently an aromatic vinyl hydrocarbon block or a conjugated diene block,

X is a functional group derived from a polymerization terminator,

m, n, and o are each independently an integer of 0 or more, m+n+o is 2 or more, and p is an integer of 1 to 3.

Specifically, the block copolymer may be a [ABC] block copolymer represented by Formula 3, and in this case, the block copolymer may be a linear, branched, symmetric, asymmetric or radial styrene-butadiene-styrene (SBS ), styrene-isoprene-styrene (SIS), or may include a styrene-butadiene double block copolymer, may be a mixture of these different types, and specifically, may be a block copolymer represented by styrene-butadiene-styrene. have.

In addition, the block copolymer may have a weight average molecular weight of 100,000 to 300,000 g/mol or 150,000 to 200,000 g/mol, and it is applied as an asphalt modifier within this range to easily improve high-temperature physical properties and solubility of asphalt. .

In addition, the present invention provides a method for producing the block copolymer.

The production method according to an embodiment of the present invention comprises the steps of polymerizing an aromatic vinyl hydrocarbon in a hydrocarbon solvent in the presence of a polymerization initiator to prepare an aromatic vinyl hydrocarbon block (S1); Polymerizing the aromatic vinyl hydrocarbon block and the conjugated diene monomer to prepare a main chain unit including the aromatic vinyl hydrocarbon block and the conjugated diene block (S2); Coupling the main chain unit and a coupling agent (S3); And mixing with a polymerization terminating agent (S4), wherein the polymerization terminating agent is at least one selected from the group consisting of compounds represented by Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3.

Hereinafter, the manufacturing method is divided into stages and described in more detail.

The aromatic vinyl hydrocarbon, the conjugated diene monomer, and the polymerization terminator used in the preparation method are as described above.

The step S1 is a step of polymerizing an aromatic vinyl hydrocarbon to prepare an aromatic vinyl hydrocarbon block polymer composed of repeating units derived from the aromatic vinyl hydrocarbon, and may be performed by polymerizing the aromatic vinyl hydrocarbon in the presence of a polymerization initiator in a hydrocarbon solvent. .

The hydrocarbon solvent is not particularly limited as long as it does not react with a polymerization initiator and is usually used in a polymerization reaction, and examples thereof include linear or branched hydrocarbon compounds such as butane, n-pentane, n-hexane, n-heptane or isooctane; Alkyl substituted or unsubstituted cyclic hydrocarbon compounds such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane, and methyl cycloheptane; And it may be one or more selected from the group consisting of alkyl substituted or unsubstituted aromatic hydrocarbon compounds such as benzene, toluene, xylene, and naphthalene.

In addition, the hydrocarbon solvent may contain a polar additive to control the vinyl content and improve the polymerization rate, and the polar additive is, for example, at least one selected from the group consisting of tetrahydrofuran, ethyl ether, tetramethyl ethylene diamine, and benzofuran. I can.

In addition, the polymerization initiator is not particularly limited as long as it is usually used for anionic polymerization, but, for example, n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allyl It may be one or more selected from the group consisting of lithium, vinyl lithium, phenyl lithium, and benzyl lithium.

The step S2 is a step for polymerizing the aromatic vinyl hydrocarbon block and the conjugated diene monomer to prepare a block copolymer chain, which is a main chain unit including an aromatic vinyl hydrocarbon block and a conjugated diene block. Can be carried out by polymerization.

As another example, the step S2 may be to polymerize the aromatic vinyl hydrocarbon block and the conjugated diene monomer in the presence of a hydrocarbon solvent and a polymerization initiator, and the hydrocarbon solvent and the polymerization initiator are as described above.

Meanwhile, the polymerization initiator used in step S1 and step S2 may be used in an amount of 0.3 mmol to 3.3 mmol based on a total of 1 mol of aromatic vinyl hydrocarbon and conjugated diene monomer, and a block copolymer can be easily prepared within this range. .

In addition, the polymerization reaction of step S1 and step S2 may be performed under a pressure range (0.1 to 10 bar) in which the reactant can be maintained in a liquid state from 0 to 150°C.

The step S3 is a coupling reaction step of coupling a main chain unit including the aromatic vinyl hydrocarbon block and a conjugated diene block, and may be performed by reacting the main chain unit with a coupling agent.

Here, the coupling agent induces coupling between main chain units, and a conventional coupling agent used for coupling of the polymer may be used, for example, selected from dimethyldichlorosilane, silicon tetrachloride, and tetramethylorthosilicate. There may be more than one type.

The step S4 is a step of coupling a functional group derived from a polymerization terminator to a main chain unit while terminating the polymerization after the coupling reaction, and may be performed by mixing a polymerization terminator.

Here, the polymerization terminator may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total monomer, and in this case, a functional group derived from the polymerization terminator in the block copolymer may be introduced in the amount as described above. Meanwhile, here, 100 parts by weight of the total monomer represents the total amount obtained by adding the aromatic vinyl hydrocarbon and the conjugated diene monomer used in the steps S1 and S2.

In addition, the present invention provides an asphalt composition comprising the block copolymer and asphalt.

The asphalt composition may include a block copolymer in an amount of 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of asphalt, and within this range, physical properties of asphalt can be effectively improved.

The asphalt is a residue obtained by refining crude oil and is mainly composed of hydrogen and carbon, and is composed of a hydrocarbon compound in which a small amount of nitrogen, sulfur or oxygen is bonded, and it is a common one that includes both natural and petroleum asphalt. I can. For example, the asphalt is natural asphalt (buton natural asphalt), straight asphalt (straight asphalt), blown asphalt (blown asphalt), goose asphalt (guss asphalt), cutback asphalt (cutback asphalt), emulsified asphalt, sebum (PG) It may be graded asphalt or the like, and specifically, it may be straight asphalt.

The straight asphalt is a final residue obtained by distilling crude oil in an atmospheric distillation column and then distilling the atmospheric residual oil under reduced pressure, and may be prepared by a conventional method or a commercially available product. The commercially available straight asphalt is AP-3 or AP-5.

In addition, the asphalt may contain 1 to 40% by weight, or 5 to 30% by weight of asphaltene based on the total content.

In addition, the asphalt composition may further include a crosslinking agent, wherein the crosslinking agent may serve to further improve the compatibility of the block copolymer and asphalt, and the crosslinking agent is particularly limited if it is a sulfur compound containing sulfur or iron sulfate. It does not, but sulfur powder is mentioned, for example.

In addition, the asphalt composition may be prepared by blending a block copolymer, asphalt, and, if necessary, a crosslinking agent with a high shear mixer and a low shear mixer.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are intended to illustrate the present invention, and that various changes and modifications can be made within the scope of the present invention and the scope of the technical idea are obvious to those skilled in the art, and the scope of the present invention is not limited thereto.

Example

Example 1

A 10 liter reactor substituted with argon was set at 50° C. and a pressure of 1 bar, and 4750 g of cyclohexane and 280 g of styrene were added, and 0.12 g of n-butyllithium was added to initiate polymerization. Thereafter, 15 minutes after the polymerization temperature of styrene reached the maximum temperature, 720 g of 1,3-butadiene was added to perform polymerization, and 10 minutes after the 1,3-butadiene polymerization temperature reached the maximum temperature, the coupling was performed. 1.0 g of ring agent dimethyldichlorosilane was added and reacted. After 10 minutes of the addition of the coupling agent, 10 g of 4-methylbenzenesulfonyl chloride, a compound represented by Formula 1, was added as a polymerization terminator, mixed, and then the polymerization was terminated, and 1 g of ethanol was added and stirred for 10 minutes. Was added to prepare a block copolymer.

Example 2

In Example 1, 10 g of 2,2,2-trichloroethyl carbonochloridate, a compound represented by Formula 2, was used instead of 4-methylbenzenesulfonyl chloride, a compound represented by Formula 1, as a polymerization terminator. Except for that, it was carried out in the same manner as in Example 1 to prepare a powdered acrylic processing aid.

Example 3

In Example 1, except that 10 g of benzothiazole-2-carbonyl chloride, a compound represented by Formula 3, was used instead of 4-methylbenzenesulfonyl chloride, a compound represented by Formula 1, as a polymerization terminator. In the same manner as in Example 1, an acrylic processing aid of powder was prepared.

Comparative example

In Example 1, an acrylic processing aid of powder was prepared by performing the same method as in Example 1, except that water was used as a polymerization terminator.

Experimental example

Softening point, phase separation temperature, viscosity, elastic recovery rate, and elongation were compared and analyzed using the asphalt composition including the block copolymer in the above Examples and Comparative Examples. The results are shown in Table 1 below.

1) Preparation of asphalt composition

In the mixing container (heating mantle) 500 g of asphalt (AP-5, SK energy) and 4.0 parts by weight of the block copolymers of Examples and Comparative Examples were added to 100 parts by weight of the asphalt, and a high shear rate of 3,000 rpm at 191°C And stirred for 1 hour. Thereafter, each asphalt composition was prepared by stirring for 4 hours, 5 hours and 6 hours at a low shear rate of 300 rpm. Here, each asphalt composition prepared by stirring for 4 hours at 300 rpm for each of the examples and comparison was stirred for 1 and 5 hours for the specimen, each asphalt composition prepared by stirring for 2 and 6 hours for the specimen. Is called Psalm 3.

2) softening point

The softening point was measured according to ASTM (American Society Testing and Materials) D36. Specifically, when heated with water or glycerin at 5°C per minute, each specimen 3 began to soften and placed on the specimen with a diameter of 9.525 mm and a weight of 3.5 g. The temperature was measured when the beads were sagging by 1 inch.

3) Phase separation temperature

Each specimen 1, specimen 2 and specimen 3, 50 g each were improved in an aluminum tube, left in an oven at 180°C for 72 hours, divided into three portions, and measured the softening points of the upper and lower portions by ASTM D36 method, and the temperature difference was measured. Calculated. At this time, if the difference in the phase separation temperature is 3°C or less, it means that it is completely dissolved, and through this, the dissolution time can be measured.

4) viscosity

The viscosity of each specimen 3 was measured at 135°C, 160°C and 180°C according to ASTM D4402 under the condition of spindle 27 using a Brookfield DV-II+ Pro Model.

5) Elastic recovery rate

The elastic recovery rate was measured according to ASTM D6083-97 after allowing the specimen 3 to stand at 25° C. for 1 hour.

6) Shinto

Elongation was measured according to ASTM D113 after allowing the specimen 3 to stand at 15° C. for 1 hour. Here, elongation refers to a property in which a material having high viscosity is elongated and broken without breaking brittleness due to tension, and a material having a low elongation is liable to cause cracks on road surfaces when applied to road pavements.

division Example Comparative example One 2 3 Softening point (℃, specimen 3) 84.6 83.9 84.9 82.5 Phase separation temperature (△T) Psalm 1 2.7 8.9 2.1 19.8 Psalm 2 1.8 2.5 1.4 11.3 Psalm 3 1.3 1.9 0.8 2.9 Elongation (mm, 5℃) 43.0 46.0 45.0 44.0 Elastic recovery rate (%) 91.5 92.5 90.5 93.0 Viscosity
(cps, Psalm 3) 135℃ 1840 1830 1865 1780 160℃ 610 595 635 560 180℃ 310 305 325 290

As shown in Table 1, the asphalt compositions of Examples 1 to 3 containing the block copolymer according to an embodiment of the present invention as a modifier exhibited equal or higher elongation, elastic recovery rate, and viscosity characteristics as compared to the comparative example, and the softening point It was confirmed that this 1.5 to 2°C was also high, and the dissolution time was 1 or 2 hours earlier. Specifically, when the phase separation temperature difference is 3° C. or less, dissolution is completed, and in Examples 1 and 3, dissolution is completed in 4 hours of stirring, and in Example, dissolution is completed in only 5 hours of stirring, compared to 6 hours of dissolution time of Comparative Example It decreased by 2 hours in time.

Through the above results, it was confirmed that the block copolymer containing the functional group derived from the polymerization terminator according to the present invention was applied as an asphalt modifier to improve the solubility and softening point of asphalt at the same time.

Claims (13)

A main chain unit comprising an aromatic vinyl hydrocarbon block composed of repeating units derived from aromatic vinyl hydrocarbons and a conjugated diene block composed of repeating units derived from conjugated diene monomers; And a functional group derived from a polymerization terminator,
A block copolymer in which the polymerization terminating agent is at least one selected from the group consisting of the following Chemical Formulas 1, 2, and 3:
[Formula 1]

[Formula 2]

[Formula 3]

.
The method of claim 1,
The functional group derived from the polymerization terminator is bonded to at least one terminal of the main chain unit.
The method of claim 1,
The polymerization terminator is a block copolymer that is a compound represented by Chemical Formula 3.
The method of claim 1,
The block copolymer is a block copolymer comprising 0.01 parts by weight to 10 parts by weight of a polymerization terminator-derived functional group based on 100 parts by weight of the total weight of the main chain unit.
The method of claim 1,
The block copolymer is a block copolymer represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
A to C are each independently an aromatic vinyl hydrocarbon block or a conjugated diene block,
X is a functional group derived from a polymerization terminator,
m, n, and o are each independently an integer of 0 or more, m+n+o is 2 or more, and p is an integer of 1 to 3.
The method of claim 1,
The aromatic vinyl hydrocarbon is one or more selected from the group consisting of styrene, alpha-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-(para-methylphenyl)styrene. Block copolymer.
The method of claim 1,
The conjugated diene monomer is at least one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimenyl-1,3-butadiene, and 2-phenyl-1,3-butadiene.
The method of claim 1,
A block copolymer having a weight average molecular weight of 100,000 g/mol to 300,000 g/mol.
The method of claim 1,
Block copolymers that are asphalt modifiers.
Polymerizing an aromatic vinyl hydrocarbon in the presence of a polymerization initiator in a hydrocarbon solvent to produce an aromatic vinyl hydrocarbon block;
Polymerizing the aromatic vinyl hydrocarbon block and the conjugated diene monomer to prepare a main chain unit including an aromatic vinyl hydrocarbon block and a conjugated diene block;
Coupling the main chain unit and a coupling agent; And
Including the step of mixing with a polymerization terminating agent,
The method for producing a block copolymer according to claim 1, wherein the polymerization terminating agent is at least one selected from the group consisting of compounds represented by the following Formulas 1, 2, and 3:
[Formula 1]

[Formula 2]

[Formula 3]

.
The method of claim 10,
The polymerization terminating agent is a method for producing a block copolymer to be used in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the total amount of monomers.
An asphalt composition comprising the block copolymer according to claim 1 and asphalt.
The method of claim 12,
The asphalt composition comprising a block copolymer of 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the total weight of the asphalt.