KR101551002B1 - Asphalt modifier and modified asphalt composition comprising the same - Google Patents

Abstract

(상기 화학식 1에서,
주쇄를 이루는 A 내지 C 블록은 서로 독립적으로 비닐 방향족 탄화수소 블록 또는 공액디엔 블록이고, 다관능성 작용기인 X는 비닐기, 히드록실기, 카르보닐기, 카르복실기, 에스테르기, 실라놀기 및 실릴기로 이루어진 군으로부터 선택된 적어도 하나 이상의 치환기를 함유하는 탄소수 1 내지 12의 선형 또는 분지형 알킬렌기이며, m, n 및 o는 1 이상의 정수이며, p는 0<p≤3의 정수이다.)The present invention relates to an asphalt modifier comprising a vinyl aromatic hydrocarbon-conjugated diene block copolymer as a main chain and having a polyfunctional functional group bonded to the main chain of the vinyl aromatic hydrocarbon-conjugated diene block copolymer, and an asphalt modifier represented by the following formula Asphalt composition.
[Chemical Formula 1]

(In the formula 1,
The main chain A to C blocks are independently a vinyl aromatic hydrocarbon block or a conjugated diene block, and the polyfunctional functional group X is a group selected from the group consisting of a vinyl group, a hydroxyl group, a carbonyl group, a carboxyl group, an ester group, a silanol group and a silyl group M, n and o are integers of 1 or more, and p is an integer of 0 < p &lt; = 3), wherein R is a linear or branched alkylene group having 1 to 12 carbon atoms,

Description

[0001] ASPHALT MODIFIER AND MODIFIED ASPHALT COMPOSITION COMPRISING THE SAME [0002]

The present invention relates to an asphalt modifier that maximizes compatibility with asphalt, and a modified asphalt composition having improved storage stability.

Asphalt is a residue of volatile oil components in petroleum crude oil which is mostly evaporated, and maintains a viscous liquid or semi-solid state at high temperature and hard hardness at a temperature below room temperature.

The asphalt is widely used for building materials such as road pavement materials and waterproofing materials because it is rich in plasticity, has high water resistance, electrical insulation, adhesiveness, and is chemically stable. However, such asphalt is subject to plastic deformation when it is exposed to high temperature for a long period of time during use and cracks due to external impact at low temperatures.

In order to solve such a problem, researches have been made to improve the physical properties of asphalt by adding various polymers.

For example, a vinyl aromatic hydrocarbon-conjugated diene block copolymer such as a styrene-butadiene-styrene (SBS) block copolymer is widely used as a modifier for improving physical properties of an asphalt composition or as an impact modifier for other resins.

On the other hand, such a block copolymer regards compatibility with asphalt as the most important property. That is, excellent compatibility with asphalt can shorten processing time and improve physical properties.

However, due to the recent rise in crude oil prices and energy conservation policies, refining facilities have been continuously upgraded, and the content of asphaltenes in asphalt, a by-product of refining, is rising. Since asphaltenes contain a large number of polar functional groups at the terminals as an aggregate of aromatic hydrocarbons, compatibility with styrene-butadiene-styrene (SBS) block copolymers having no polar functional groups is very poor. Therefore, not only the processing time or the production time of the asphalt composition is greatly extended but also the quality of the asphalt is deteriorated by lowering the elasticity of the modified asphalt composition.

In order to improve the compatibility of the asphalt with the styrene-butadiene-styrene (SBS) block copolymer, the molecular weight of the styrene-butadiene-styrene block copolymer can be controlled or the coupling efficiency A method of changing the molecular microstructure of the coalescence or adding an additive such as oil as a processing aid has been proposed.

However, even when such a method is applied, a method for manufacturing each modified asphalt must be developed for various asphalt having quality variations, and thus, it is not the ultimate solution.

Therefore, it is urgent to develop an asphalt modifier excellent in compatibility with asphalt.

In order to solve the problems of the prior art described above, the present invention provides an asphalt modifier that maximizes compatibility with asphalt by introducing a polar functional group into the vinyl aromatic hydrocarbon-conjugated diene block copolymer main chain, This improved modified asphalt composition is provided.

Specifically, the present invention provides an asphalt modifier comprising a vinyl aromatic hydrocarbon-conjugated diene block copolymer as a main chain and having a polyfunctional functional group bonded to the vinyl aromatic hydrocarbon-conjugated diene block copolymer main chain, to provide.

[Chemical Formula 1]

(In the formula 1,

The main chain A to C blocks are independently a vinyl aromatic hydrocarbon block or a conjugated diene block, and the polyfunctional functional group X is a vinyl group, a hydroxyl group, a carbonyl group, a carboxyl group, an ester group, a silanol group, a linear or branched alkylene group having 1 to 12 carbon atoms and containing at least one substituent selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, to be.)

Also, the present invention provides a modified asphalt composition comprising the asphalt modifier, the asphalt and the crosslinking agent.

As described above, according to the present invention, a multifunctional functional group is introduced into a styrene-butadiene-styrene (SBS) block copolymer to provide an asphalt modifier excellent in compatibility with asphalt, To thereby provide an asphalt composition having greatly improved storage stability and the like.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and together with the description of the invention serve to further the understanding of the technical idea of the invention, It should not be construed as limited.
1 is a fluorescence microscope photograph (A) in which the functionalized block copolymer is completely dissolved in the asphalt composition of the present invention and a state (B) in which the functionalized block copolymer is completely dissolved (400 Measured at a magnification).

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

Herein, terms and words used in the present specification and claims should not be construed to be limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of the term to describe its own invention in the best way. It should be construed as meaning and concept consistent with the technical idea of the present invention.

First, the present inventors have found that an asphalt modifier comprising a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer, such as a functionalized styrene-butadiene block copolymer, by bonding a multifunctional functional group can be obtained by reacting a conventional styrene-butadiene block copolymer It was confirmed that the storage stability of the modified asphalt composition was greatly improved under the same production time by shortening the dissolving time while realizing high temperature and low temperature physical properties equivalent to conventional ones in the asphalt composition, Thereby completing the invention.

asphalt Modifier

Specifically, in an embodiment of the present invention, a vinyl aromatic hydrocarbon-conjugated diene block copolymer having a vinyl aromatic hydrocarbon-conjugated diene block copolymer as a main chain and having a polyfunctional functional group bonded to a main chain of the vinyl aromatic hydrocarbon- Asphalt modifier is provided.

[Chemical Formula 1]

(In the formula 1,

The main chain A to C blocks are independently a vinyl aromatic hydrocarbon block or a conjugated diene block, and the polyfunctional functional group X is a group selected from the group consisting of a vinyl group, a hydroxyl group, a carbonyl group, a carboxyl group, an ester group, a silanol group and a silyl group M, n and o are integers of 1 or more, and p is an integer of 0 < p &lt; = 3), wherein R is a linear or branched alkylene group having 1 to 12 carbon atoms,

In the vinyl aromatic hydrocarbon-conjugated diene block copolymer (asphalt modifier represented by Chemical Formula 1) to which the polyfunctional functional group is bonded according to the present invention, the vinyl aromatic hydrocarbon block is selected from the group consisting of styrene, alpha-methylstyrene, And at least one member selected from the group consisting of methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and 4- (para-methylphenyl) styrene.

The conjugated diene block may include at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-phenyl-1,3-butadiene.

In addition, the polyfunctional functional group X of the present invention may be a mixture of different compounds independently of each other. For example, the polyfunctional functional group X is a linear or branched alkylene group having 1 to 10 carbon atoms containing at least one substituent selected from the group consisting of a vinyl group, a hydroxyl group, a carbonyl group, a carboxyl group and an ester group, An alkylene group and a linear or branched alkylsilanol group or alkylsilyl group having 1 to 4 carbon atoms. That is, the asphalt modifier represented by Formula 1 of the present invention may further include a compound having a polyfunctional functional group, which is a linear or branched alkylsilanol group or alkylsilyl group having 1 to 4 carbon atoms in addition to the alkylene group.

In the asphalt modifier of the present invention, the multifunctional functional group is derived from a coupling agent. Specifically, the multifunctional functional group is a vinyl aromatic hydrocarbon which can be used as a coupling agent and an asphalt modifier in the presence of an initiator such as an organometallic compound or a living anion Block and a conjugated diene block may be formed by polymerization of a cross-aligned vinyl aromatic hydrocarbon-conjugated diene block copolymer.

Wherein the initiator comprises an organometallic compound and the living anion comprises a polymer chain having an anionic end initiated from the initiator.

At this time, the organometallic compound as the initiator is not particularly limited, but typical examples thereof include n-butyllithium, sec-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allylithium, vinyllithium, Benzyl lithium, or a mixture of two or more thereof.

The organometallic compound may be included in an amount of 0.3 to 3.3 mmol based on the total amount (100 g) of the vinyl aromatic hydrocarbon block. If the content of the initiator is less than 0.3 mmol, it may be difficult to introduce the polyfunctional functional group because the molecular weight of the initiator is less than 0.3 mmol and the reactivity with the coupling agent is poor due to poor stirring efficiency of the reactor. There is a drawback that the productivity may be seriously degraded.

The coupling agent used in the polymerization reaction may be one or a mixture of two or more selected from the group consisting of glycidyl methacrylate (GMA) and dimethyldichlorosilane (DMDCS) Glycidyl methacrylate.

In the polymerization reaction, the mixing ratio (molar ratio) of the initiator to the coupling agent may be 1: 0.1 to 1, and an asphalt modifier capable of improving the storage stability of the asphalt composition with excellent compatibility with the asphalt within the range Can be manufactured. If the content of the coupling agent is less than 0.1 or more than 1, the vinyl aromatic hydrocarbon-conjugated diene block copolymer may not be produced in the form of pellets in solid polymer form, or the productivity may be seriously deteriorated.

In the above polymerization reaction, the vinyl aromatic hydrocarbon-conjugated diene block copolymer in which the vinyl aromatic hydrocarbon block and the conjugated diene block are crossed includes a vinyl aromatic hydrocarbon block in at least one block of the A and C blocks in the above formula .

In this case, the weight ratio of the vinyl aromatic hydrocarbon block to the conjugated diene block in the vinyl aromatic hydrocarbon-conjugated diene block copolymer may be 20 to 50:50 to 80. Since the block copolymer within this range can secure excellent solubility in asphalt, the asphalt composition containing the asphalt modifier of the present invention can have excellent storage stability.

Specifically, in the asphalt initiator represented by the general formula (1) comprising the vinyl aromatic hydrocarbon-conjugated diene block copolymer to which the polyfunctional functional group of the present invention is bonded, when the polyfunctional functional group is p = 1, 2e to 2g when p = 2, and compounds of formula 2h when p = 3.

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

(In the above formulas (2a) to (2h)

* Is a moiety capable of bonding with a vinyl aromatic hydrocarbon block or a conjugated diene block unit in the vinyl aromatic hydrocarbon-conjugated diene block copolymer, wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer having 1 to 3 molecules per one polyfunctional functional group Can be combined.)

In this case, the content of the polyfunctional functional group in the asphalt modifier may be 40 to 4,700 ppm, specifically 100 to 3,500 ppm, based on the total weight of the block copolymer. Within this range, the compatibility with asphalt and the storage stability effect are excellent.

The weight average molecular weight of the asphalt modifier including the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer represented by the formula (1) of the present invention may be 30,000 to 500,000 g / mol, specifically 50,000 to 500,000 g / mol, and more specifically from 50,000 to 350,000 g / mol.

In addition, embodiments of the present invention can provide a method for manufacturing an asphalt modifier comprising a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer, including the following steps.

Introducing a hydrocarbon solvent and a vinyl aromatic hydrocarbon monomer into the reactor;

Mixing the organometallic compound as the initiator and the conjugated diene monomer with stirring to prepare a vinyl aromatic hydrocarbon-conjugated diene block copolymer;

Mixing the vinyl aromatic hydrocarbon-conjugated diene block copolymer with a coupling agent to perform a coupling reaction; And

And water or alcohol is added to the reactor to remove the activity of the active polymer.

In this method, the hydrocarbon solvent may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, xylene and naphthalene- Preferably n-hexane, cyclohexane or a mixture thereof.

In addition, a polar solvent may be further added to the hydrocarbon solvent so as to control the vinyl content of the conjugated diene polymer and improve the polymerization rate. Typical examples of the polar solvent may include at least one selected from the group consisting of tetrahydrofuran, ethyl ether, tetramethylethylenediamine, and benzofuran, and more preferably tetrahydrofuran.

Here, in the above method, the content of the vinyl aromatic hydrocarbon monomer and the conjugated diene monomer may be used in an amount such that the vinyl aromatic hydrocarbon-conjugated diene block copolymer is contained in the hydrocarbon solvent in an amount of 1 to 30% by weight.

The organometallic compound may be contained in an amount of 0.3 to 3.3 mmol based on 100 g of the total amount of the vinyl aromatic hydrocarbon-conjugated diene block copolymer.

The mixing ratio (molar ratio) of the initiator: coupling agent may be 1: 0.1 to 1.

Also, in the above method, it is preferable that the polymerization reaction is carried out at 0 to 150 ° C and at a consumption rate of the conjugated diene monomer of 99% or more under a pressure range (0.1 to 10 bar) in which the reactant can be maintained in a liquid state .

Further, in the coupling reaction step, the conjugated diene blocks between the block copolymers may be connected to each other to perform a functionalization reaction (see the following reaction formula 1).

[Reaction Scheme 1]

Asphalt composition

In addition, embodiments of the present invention provide a modified asphalt composition comprising an asphalt modifier, asphalt and a crosslinking agent of the present invention.

Specifically, the modified asphalt composition may contain 1 to 10 parts by weight of an asphalt modifier, 87 to 98.95 parts by weight of asphalt, and 0.05 to 3 parts by weight of a crosslinking agent. Within this range, excellent storage stability of the asphalt composition can be secured. If the content of the asphalt modifier exceeds the above range, the manufacturing cost of the modified asphalt composition increases, and when the content of the cross-linking agent exceeds the above range, the modified asphalt becomes less elastic due to excessive cross-linking reaction, gelation. On the other hand, when the content of each of the asphalt modifier and the cross-linking agent is less than the above range, the asphalt modifying degree is low and the physical properties and elasticity of the modified asphalt are deteriorated.

At this time, the asphalt may contain 1 to 40%, particularly 5 to 30%, of asphaltenes in the total content.

The crosslinking agent is not particularly limited as long as it is a sulfur compound containing sulfur or iron sulfate, and representative examples thereof include a sulfur element.

When the modifier is contained in an amount of about 4 to 5% by weight under vulcanization conditions, the asphalt composition preferably has a melting rate of 1 to 6 hours, more preferably 1 to 3 hours. That is, the balance of physical properties of the asphalt composition is excellent within this range.

The modified asphalt composition of the present invention may have a viscosity range of a softening point of 65 ° C, an elongation of 20 cm or more, and a viscosity of 3,000 cPs or less. At this time, the elongation and viscosity are not limited to any specific range, and the elongation may be as large as 20 cm or more, and the viscosity may be preferably as small as 3,000 cPs or less. For example, the elongation may range from 20 cm to 80 cm, and the viscosity may range from 500 cPs to 3,000 cPs, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. It should be noted, however, that the examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example

asphalt Modifier  Produce

(Example 1)

4.444 g of purified cyclohexane and 313 g of styrene were charged into a 10 L reactor purged with nitrogen, and the temperature was raised to 60 캜 with stirring. To the mixed solution of cyclohexane and styrene was added 1.04 g of n-butyllithium at 50 DEG C to polymerize the styrene block. Then, 697 g of butadiene was added thereto and the mixture was polymerized until the butadiene completely consumed.

After completion of the polymerization reaction, 1.15 g of glycidyl methacrylate was added as a coupling agent to carry out a coupling reaction to prepare a polymer in which the glycidyl methacrylate was substituted with a terminal butadiene group. Subsequently, 0.2 g of water was added as a reaction terminator to remove the reaction activity.

Subsequently, when the reaction activity was removed, 3 g of an antioxidant Irganox 1076 (Ciba Specialty Chemicals Co.) and 5.8 g of TNPP (Adeka Chemical Co.) were added to the polymerization solution to give a weight average molecular weight of 112,000 g / mol, 31% by weight of a functionalized linear styrene-butadiene block copolymer.

The weight average molecular weight of each polymer pellet sample was determined by dissolving each polymer pellet sample in tetrahydrofuran (THF) for 30 minutes, loading the polymer pellets on GPC (Gel Permeation Chromatography, waters), and comparing them with the standard molecular weight of the polystyrene standard The molecular weight was measured.

Next, in order to recover only the polymer from the reaction solution, generally a stripping process is performed. Specifically, 0.7 g of Tamol (BASF) as a dispersant and 0.5 g of CaCl ₂ were added to 3 L of water and boiled. The polymer solution was slowly added to boiling water slowly to coagulate the polymer in water. Then, To 20 mm in size and the solvent was evaporated to recover the polymer. The recovered polymer was dried in an oven at 60 ° C for 16 hours to prepare a functionalized styrene-butadiene block copolymer pellet (1).

(Example 2)

The procedure of Example 1 was repeated except that 0.65 g of glycidyl methacrylate and 0.54 g of dichlorodimethylsilane were used in place of 1.15 g of glycidyl methacrylate as the coupling agent in Example 1, Functionalized linear styrene-butadiene block copolymer pellets (2) having a weight average molecular weight of 104,000 g / mol and a styrene block content of 31% by weight were prepared.

(Comparative Example 1)

The weight average molecular weight was 105,000 g / mol in the same manner as in Example 1, except that 0.98 g of dichlorodimethylsilane was used instead of 1.15 g of glycidyl methacrylate as the coupling agent in Example 1, A styrene-butadiene block copolymer pellet having a styrene block content of 31 wt% was prepared.

Preparation of modified asphalt composition

(Example 3)

500 g of asphalt (SK AP-5) was charged into the mixing container and 23.36 g of the functionalized styrene butadiene block copolymer of Example 1 was added thereto while stirring at 2,000 rpm at 160 캜. The mixture was stirred at 2500 rpm for 50 minutes while raising the temperature to 180 DEG C, and 0.53 g of a sulfur compound as a crosslinking agent was added to the mixture, followed by further stirring for 10 minutes. Subsequently, the stirring speed was lowered at 300 rpm and further stirred for 1 hour to prepare the modified asphalt composition (1) of the present invention.

(Example 4)

Except that the functionalized styrene-butadiene block copolymer of Example 2 was used in place of the functionalized styrene-butadiene block copolymer of Example 1, the modified asphalt composition of the present invention 2).

(Comparative Example 2)

A modified asphalt composition was prepared in the same manner as in Example 3, except that the styrene-butadiene block copolymer of Comparative Example 1 was used instead of the functionalized styrene-butadiene block copolymer of Example 1 above.

(Experimental Example)

Properties of each of the modified asphalt compositions prepared in Examples 3 and 4 and the modified asphalt composition of Comparative Example 2 were measured by the following methods, and the results are shown in Table 1 below.

(1) Observation of morphology

The morphology of the styrene-butadiene block copolymer was observed and the modified asphalt shape at 400 magnification was observed with a fluorescence microscope (Nikon) to determine the degree of dissolution to the asphalt. The results of the observation with a fluorescence microscope are shown in Fig.

As shown in Fig. 1, it was confirmed that the size of the yellow particles corresponding to the styrene block of the styrene-butadiene block copolymer was small and uniform in the state (B) which was well dissolved compared with the state (A) A total dissolving time of 2 hours was required until it reached the state (B).

Based on this, the production time of the modified asphalt compositions of Examples 3 to 4 and Comparative Example 2 was set to a total of 2 hours. In addition, the degree of dissolution was quantitatively reaffirmed through the following storage stability evaluation.

(2) Softening point

The softening point is a measure of the high temperature properties of modified asphalt measured according to ASTM (American Society for Testing and Materials) D36. The specimen begins to soften by heating water or glycerin at 5 ° C / min. The temperature was measured when 3.5 g of beads were squeezed by 1 inch.

(3) Shindo

The elongation (5 ° C) is a low temperature property measure of modified asphalt measured according to ASTM D 113. The elongation length was measured until the specimen was pulled in both directions in a thermostatic chamber maintained at 5 ° C.

(4) Viscosity

The viscosity (135 占 폚) was measured according to ASTM D4402 under the condition of spindle 27 using Brookfield DV-II + Pro Model. Generally, when the measured value exceeds 3,000 cPs, it is evaluated that the workability in the production of modified asphalt is lowered.

(5) Storage stability

The storage stability was evaluated by changing 50 g of the modified asphalt composition in an aluminum tube, leaving it in an oven at 163 캜 for 48 hours, leaving it in a cooler at -5 캜 for 4 hours or more, and then measuring the softening point at the upper part and the lower part, . In general, it is said that phase separation does not occur when the temperature difference is within 2.5 ° C, and the smaller the difference is, the better the storage stability is.

(6) Properties after RTFP

The properties after RTFP are one of the methods for evaluating physical properties after aging. Hot air containing oxygen is injected into a 1600 ° C RTFO (Rolling thin film oven), the glass bottle containing 35 g of the modified asphalt composition is rotated for 85 minutes, Then, the softening point was measured according to the method of ASTM D36 by the method of ASTM D113 (5 캜).

division Example 3 Example 4 Comparative Example 2 RTFO pre-property Softening point (℃) 85.4 83.7 85.7 Elongation (5 캜, cm) 23.9 25.2 23.9 Viscosity (135 ° C, cPs) 1810 1775 1895 Storage stability (ΔT) 4.8 2.4 10.2 Properties after RTFO Softening point (℃) 69.2 75.9 78.4 Elongation (5 캜, cm) 12.1 11.0 11.5

As shown in Table 1, the modified asphalt compositions of Examples 3 and 4 of the present invention had a storage stability of 5% without deteriorating the basic properties of modified asphalt such as softening point, elongation, and viscosity, as compared with the modified asphalt composition of Comparative Example 2 To &lt; RTI ID = 0.0 &gt; 8 C, &lt; / RTI &gt; That is, unlike Comparative Example 2, the storage stability of Examples 3 and 4 is excellent, and it is expected that the quality of the modified asphalt will be maintained stably while transporting the modified asphalt composition to the road pavement area.

In particular, in the case of the modified asphalt composition of Example 4 comprising a styrene-butadiene block copolymer having a multifunctional functional group introduced using two or more kinds of coupling agents, styrene -Butadiene block copolymer, the softening point and the storage stability after RTFO are superior to those of the modified asphalt composition of Example 3.

Claims (27)

Vinyl aromatic hydrocarbon-conjugated diene block copolymer as a main chain,
An asphalt modifier represented by the following formula (1), which comprises a polyfunctional functional group bonded to the vinyl aromatic hydrocarbon-conjugated diene block copolymer main chain;
[Chemical Formula 1]

(In the formula 1,
The main chain A to C blocks are independently a vinyl aromatic hydrocarbon block or a conjugated diene block, and the polyfunctional functional group X is a group selected from the group consisting of a vinyl group, a hydroxyl group, a carbonyl group, a carboxyl group, an ester group, a silanol group and a silyl group M, n and o are integers of 1 or more, and p is an integer of 0 <p? 3.
The method according to claim 1,
The vinyl aromatic hydrocarbon block may be at least one selected from the group consisting of styrene, alpha-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene and 4- (para- And an asphalt modifier.
The method according to claim 1,
Wherein the conjugated diene block comprises at least one member selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-phenyl-1,3-butadiene. .
The method according to claim 1,
Wherein the polyfunctional functional group X is a linear or branched alkenylene group having 1 to 10 carbon atoms and containing at least one substituent selected from the group consisting of a vinyl group, a hydroxyl group, a carbonyl group, a carboxyl group and an ester group.
The method of claim 4,
Wherein the polyfunctional functional group X further comprises at least one compound selected from the group consisting of a linear or branched alkylsilanol group having 1 to 4 carbon atoms and an alkylsilyl group.
The method according to claim 1,
Wherein said multifunctional functional group is derived from a coupling agent.
The method of claim 6,
The polyfunctional functional group may be a vinyl aromatic hydrocarbon-conjugated diene block copolymer in which a vinyl aromatic hydrocarbon block and a conjugated diene block, which are usable as a coupling agent and an asphalt modifier in the presence of an initiator such as an organometallic compound or a living anion, Wherein the asphalt modifier is formed by polymerization reaction.
The method of claim 6,
Wherein the coupling agent comprises one or a mixture of two or more selected from the group consisting of glycidyl methacrylate (GMA) and dimethyldichlorosilane (DMDCS).
The method of claim 7,
Wherein the initiator comprises an organometallic compound and the living anion comprises a polymer chain having an anionic end initiated from the initiator.
The method of claim 7,
The initiator may be a single substance selected from the group consisting of n-butyl lithium, sec-butyl lithium, methyl lithium, ethyl lithium, isopropyl lithium, cyclohexyl lithium, allyl lithium, vinyl lithium, phenyl lithium, Asphalt modifier.
The method of claim 7,
Wherein the mixing ratio (molar ratio) of the initiator to the coupling agent is 1: 0.1 to 1. The asphalt modifier according to claim 1,
The method according to claim 1,
The asphalt modifier according to claim 1, wherein at least one of the A and C blocks comprises a vinyl aromatic hydrocarbon block.
The method according to claim 1,
Wherein the weight ratio of the vinyl aromatic hydrocarbon block to the conjugated diene block in the vinyl aromatic hydrocarbon-conjugated diene block copolymer is 20 to 50:50 to 80. The asphalt modifier according to claim 1,
The method according to claim 1,
Wherein the polyfunctional functional group X is represented by the following formulas (2a) to (2h).
(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

(In the above formulas (2a) to (2h)
* Is a moiety capable of bonding with a vinyl aromatic hydrocarbon block or a conjugated diene block unit in the vinyl aromatic hydrocarbon-conjugated diene block copolymer, wherein 1 to 3 molecules of the vinyl aromatic hydrocarbon-conjugated diene block copolymer per molecule of the polyfunctional functional group Can be combined.)
The method according to claim 1,
Wherein the content of the polyfunctional functional group in the asphalt modifier is 40 to 4,700 ppm based on the total weight of the block copolymer.
The method according to claim 1,
Wherein the asphalt modifier has a weight average molecular weight of 30,000 to 500,000 g / mol.
Introducing a hydrocarbon solvent and a vinyl aromatic hydrocarbon monomer into the reactor;
Mixing the organometallic compound as the initiator and the conjugated diene monomer with stirring to prepare a vinyl aromatic hydrocarbon-conjugated diene block copolymer;
Mixing the vinyl aromatic hydrocarbon-conjugated diene block copolymer with a coupling agent to perform a coupling reaction; And
And removing the activity of the active polymer by injecting water or alcohol into the reactor.
18. The method of claim 17,
Wherein the coupling agent is a mixture of one or two selected from the group consisting of glycidyl methacrylate (GMA) and dimethyldichlorosilane (DMDCS).
18. The method of claim 17,
Wherein said hydrocarbon solvent comprises at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, xylene and naphthalene- Way.
The method of claim 19,
Wherein the hydrocarbon solvent further comprises a polar solvent.
The method of claim 20,
Wherein the polar solvent is at least one selected from the group consisting of tetrahydrofuran, ethyl ether, tetramethylethylenediamine and benzofuran.
A modified asphalt composition comprising the asphalt modifier, asphalt and a cross-linking agent according to claim 1.
23. The method of claim 22,
Wherein the modified asphalt composition comprises 1 to 10 parts by weight of an asphalt modifier, 87 to 98.95 parts by weight of asphalt, and 0.05 to 3 parts by weight of a crosslinking agent.
23. The method of claim 22,
Wherein the asphalt comprises 1 to 40% of asphaltenes in the total amount of the asphalt composition.
23. The method of claim 22,
Wherein the cross-linking agent comprises a sulfur compound containing sulfur or iron sulphate.
23. The method of claim 22,
Wherein the asphalt composition has a melting rate of 1 to 6 hours based on the modifier when the modifier is contained in an amount of about 4 to 5% by weight.
23. The method of claim 22,
Wherein the modified asphalt composition has a viscosity range of a softening point of 65 占 폚, an elongation of 20 cm or more, and a viscosity of 3,000 cPs or less.

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