KR101540498B1 - Polymer modifiers for aspalt, and asphalt compositon containing the same - Google Patents

Abstract

The present invention relates to a polymer modifier for asphalt and an asphalt composition containing the same, and is characterized in that it is functionalized without lowering the molecular weight and is excellent in compatibility with asphalt, thereby drastically shortening the dissolution time of the asphalt composition, There is provided an effect of providing a vinyl aromatic hydrocarbon-conjugated diene block copolymer, a method of producing the vinyl aromatic hydrocarbon-conjugated diene block copolymer, and an asphalt composition comprising the vinyl aromatic hydrocarbon-conjugated diene block copolymer.

Description

POLYMER MODIFIERS FOR ASPALT AND ASPHALT COMPOSITON CONTAINING THE SAME Technical Field [1] The present invention relates to a polymer modifier for asphalt,

The present invention relates to a polymer modifier for asphalt and a composition containing the same. More specifically, the present invention relates to a polymer modifier for asphalt, which is functionalized without deteriorating the molecular weight and is excellent in compatibility with asphalt to drastically shorten the dissolution time of the asphalt composition, The present invention relates to a polymer modifier for asphalt having a shortened dissolution time while maintaining a balance of physical properties at the time of use.

The block copolymer is widely used as a modifier for improving physical properties of an asphalt composition or as an impact modifier for other resins. In particular, the vinyl aromatic hydrocarbon-conjugated diene block copolymer is widely used as an asphalt modifier.

The most important properties of the block copolymer used as an asphalt modifier are compatibility with asphalt. Excellent compatibility with asphalt can shorten processing time and improve physical properties.

The asphalt consists largely of four components, of which the worst compatibility with the block copolymer is asphaltenes. Since asphaltenes contain a large number of hydrophilic functional groups at the ends thereof as an aggregate of aromatic hydrocarbons, they are poorly compatible with block copolymers having no hydrophilic functional groups, and thus are components that greatly prolong the processing time or production time of the asphalt composition.

Therefore, in order to improve the compatibility with asphalt, studies have been conducted to introduce a hydrophilic functional group into a block copolymer. Representative examples thereof include a method in which a vinyl aromatic hydrocarbon-conjugated diene block copolymer and a hydrophilic monomer are mixed in an extruder at a high temperature to introduce a hydrophilic functional group into the branch of the block copolymer.

However, this method has a limitation in that expensive manufacturing equipment must be additionally installed, and uniform functionalization within the block copolymer is difficult. Particularly, a block copolymer composed of a vinyl aromatic hydrocarbon-conjugated diene can be partially oxidized under high temperature and high pressure conditions in an extruder, and further, the polymer chain is broken, resulting in a decrease in molecular weight and a serious deterioration of physical properties.

Therefore, it is urgently required to develop a block copolymer for an asphalt modifier that is excellent in compatibility and is functionalized without lowering the molecular weight.

It is an object of the present invention to provide a polymer modifier for asphalt having a shortened dissolution time while maintaining a balance of physical properties and a composition containing the same.

In order to achieve the above object, the present invention provides a vinyl aromatic hydrocarbon-conjugated diene block copolymer added to asphalt, wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer has a 1,4 structure, Structure, and an aldehyde structure, wherein the aldehyde structure comprises a vinyl 1,2 structure partially oxidized by an oxidative reaction or an electrical acrylic discharge to within a range of 40 to 1740 ppm,
The vinyl aromatic hydrocarbon vinyl-conjugated diene block copolymer has a molecular weight ratio (before oxidation block copolymer / oxidation post block copolymer) of 1.004-1.106 before and after oxidation,
Wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer is added to the asphalt so that the dissolution time, softening point and elongation of the asphalt satisfy the following formula.
[Formula 1]
148.59 ≤ AB / C < 206.75
B is the dissolution time (min) until the softening point difference in the storage stability test is measured within 2.5 占 폚, and C is the melting point measured by ASTM D113 at 5 占 폚 (Mm).

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The present invention also provides an asphalt composition comprising the polymer modifier for asphalt.

Further, in the production of such a polymer modified asphalt, the step of dissolving the asphalt composition at a high temperature of 150 to 220 ° C, wherein the measured dissolution time, softening point and elongation of the asphalt satisfy the following formula A method for producing a polymer modified asphalt is provided.

[Formula 1]

148.59 ≤ AB / C < 206.75

B is the dissolution time (min) until the softening point difference in the storage stability test is measured within 2.5 占 폚, and C is the melting point measured by ASTM D113 at 5 占 폚 (Mm).

As described above, according to the present invention, the composition of the present invention is functionalized without lowering the molecular weight and is excellent in compatibility with asphalt, so that the dissolution time of the asphalt composition is remarkably shortened and the dissolution time is shortened while maintaining balance of physical properties when mixed with asphalt A polymer modifier for asphalt, and a composition comprising the same.

FIG. 1 is a microphotograph of a state in which the functionalized block copolymer in the asphalt composition of the present invention is completely dissolved and a state in which the functionalized block copolymer is completely dissolved, at a magnification of 400 times.
2 is a graph showing the change in spectra according to the degree of functionalization of the ¹ H NMR spectrum of the block copolymer of Comparative Example 1 and the ¹ H NMR spectrum of the block copolymer prepared by reacting the aldehyde functionalization for 2 hours in Example 6 And the change in the major ¹ H NMR peak.

Hereinafter, the present invention will be described in detail.

The asphalt polymer modifier to be provided according to the present invention is a vinyl aromatic hydrocarbon-conjugated diene block copolymer to be added to asphalt, wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer has a dissolution time, softening point and elongation of asphalt satisfying the following formula As a technical feature.

[Formula 1]

148.59 ≤ AB / C < 206.75

B is the dissolution time (min) until the softening point difference in the storage stability test is measured within 2.5 占 폚, and C is the melting point measured by ASTM D113 at 5 占 폚 (Mm).

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Further, the vinyl aromatic hydrocarbon-conjugated diene block copolymer preferably has a weight average molecular weight within the range of 80,000 to 3,000,000 g / mol.

But are not limited to, vinyl aromatic hydrocarbons such as styrene, alpha-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- ) Styrene and 1-vinyl-5-hexyl naphthalene, and the butadiene block is preferably at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, Butadiene, isoprene, isoprene, naphthalene, naphthalene, naphthalene, naphthalene, naphthalene,

 These vinyl aromatic hydrocarbons and the conjugated dienes are preferably in a weight ratio of 5:95 to 40:60. The vinyl aromatic hydrocarbons may be selected from the group consisting of styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- Hexyne naphthalene, and the like, more preferably at least one selected from the group consisting of styrene.

The conjugated diene is preferably a copolymer comprising 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, , And more preferably at least one selected from the group consisting of 1,3-butadiene.

Particularly, the vinyl aromatic hydrocarbon-conjugated diene block copolymer is characterized by being represented by the following general formula (1).

(Wherein A to D are independently CH ₂ -CH = CH-CH or CH ₂ -CH when the butadiene is used as the conjugated diene (provided that all of A to D are CH ₂ -CH = CH-CH, may be CH ₂ -CH is one of N), W ~ Z is a, B, C or H when D is a CH ₂ -CH = CH-CH, a vinyl group, or an aldehyde group when the CH ₂ -CH, D, e, f, and g represent the number ratio of 1,4 structure, vinyl 1,2 structure and aldehyde structure, the 1,4 structure is 605,622 to 606,796 ppm, and the vinyl 1,2 structure is 76,608 To 77,269 ppm, the aldehyde structure is 40 to 1,764 ppm, G is a vinyl aromatic hydrocarbon, p is an integer number ratio of vinyl aromatic hydrocarbons to A, B, C and D, and the vinyl aromatic hydrocarbon and the conjugated diene Is in the range of 5:95 to 40:60 and F is a vinyl aromatic hydrocarbon block, H, CH ₂ CHO, CH ₂ COOH or a coupling group, and either WZ or F One having an aldehyde group, q being 1 to 10 as the number of arms centered on F, said coupling group being a group derived from a coupling agent,

The above A to D include those in which at least one of the hydrogens present on CH ₂ -CH = CH-CH or CH ₂ -CH is substituted with a substituent such as an alkyl group or the like.

The [G] p- may preferably be a vinyl aromatic hydrocarbon block.

Q is preferably 1 to 4, provided that q is 1 when F is H, CH ₂ CHO or CH ₂ COOH and 1 or 2 when F is a vinyl aromatic hydrocarbon block.

The coupling group is derived from a coupling agent and is produced by a coupling reaction of a polymer and a coupling agent.

The vinyl aromatic hydrocarbon-conjugated diene block copolymer of the formula (1) of the present invention is not particularly limited as long as it can be used as an asphalt modifier. However, a specific example of the vinyl aromatic hydrocarbon-conjugated diene block copolymer is a vinyl aromatic hydrocarbon and a conjugated diene And the polymerization is continued until the consumption rate of the monomer is 99% or more at a temperature of -5 to 150 ° C and a pressure range (0.1 to 10 bar) in which the reactant can be maintained in a liquid phase. Adding conjugated diene blocks between the prepared block copolymers, and then removing the activity of the active polymer by adding water or an alcohol and terminating the polymerization.

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

The polar solvent may be added to the hydrocarbon solvent, which serves to control the content of the vinyl 1,2 structure and improve the polymerization rate during the polymerization of the conjugated diene. The polar solvent may be at least one selected from the group consisting of tetrahydrofuran, ethyl ether, tetramethylethylenediamine and benzofuran, and more preferably tetrahydrofuran.

The organic lithium compound is preferably an alkyl lithium compound, more preferably an alkyl lithium compound having an alkyl group having 3 to 10 carbon atoms. The organic lithium compound may be, for example, methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium or tert-butyl lithium,

These vinyl aromatic hydrocarbon-conjugated diene block copolymers may preferably be composed of a triblock copolymer and a diblock copolymer. In this case, the vinyl aromatic hydrocarbon-conjugated diene block copolymer has excellent solubility in asphalt and excellent physical properties.

The triblock copolymer is a copolymer having two or more diblock copolymers bonded by a coupling agent, and the diblock copolymer is a copolymer composed of a vinyl aromatic hydrocarbon block and a conjugated diene block which are not coupled by a coupling agent . Preferably, the triblock copolymer is 40 wt.% To less than 100 wt.% And the diblock copolymer is more than 0 wt.% To 60 wt.%, More preferably the triblock copolymer is 50 wt.% To 99 wt. And 1 to 50% by weight of the diblock copolymer. Within this range, the diblock copolymer has excellent solubility in asphalt and excellent physical properties.

The oxidation is preferably carried out by an oxidation reaction or an electric acrylic discharge. In this case, the vinyl 1,2 structure in the conjugated diene block is preferentially oxidized to generate an aldehyde group and a metal catalyst used for the hydroformylation It has excellent effect on the thermal stability and discoloration of the product.

Further, as the vinyl aromatic hydrocarbon-conjugated diene block copolymer, it may be preferable to be coupled with a coupling agent. As the coupling agent, at least one of methylcitrate, methylcyclohexylmethylsilane, methyldichlorosilane and the like can be selected and used. Preferably, methylcyclohexylmethane and dichloromethylsilane are used.

The coupling may preferably have an efficiency of 40 to 100%. Within this range, the coupling is excellent in compatibility with asphalt and excellent in high temperature and low temperature properties of the asphalt composition.

Such an asphalt modifier is characterized by having a peak in the ppm range of 9.6 to 9.9 in NMR (nuclear magnetic resonance) analysis (see FIG. 2).

The asphalt composition of the present invention is characterized by comprising the above modifier and asphalt. The asphalt preferably contains asphaltenes. In this case, the physical properties of the asphalt modifier and the softening point of the asphalt modifier are improved but the production time or processing time is increased.

The weight mixing ratio of the modifier to the asphalt is preferably 0.1: 99.1 to 20:80, more preferably 1:99 to 10:90. In this case, an excellent effect of the processing time, storage stability and physical properties of the asphalt composition have.

The storage stability can be evaluated by comparing the softening point of each sample with the method of ASTGTO (American Association of State Highway and Transportation Officials) PP5 and measuring the respective softening point by ASTM D36 method. The smaller the difference, the better the storage stability.

The asphalt composition preferably has a melt speed of 6 to 15 hours, more preferably 8 to 13 hours, based on the nonvolatile (no vulcanizing agent) containing 5% by weight of the modifier, Within this range, the balance of physical properties of the asphalt composition is excellent.

Finally, the method for producing the polymer-modified asphalt according to the present invention comprises dissolving the asphalt composition at a high temperature (150 to 220 ° C), wherein the measured dissolution time, softening point and elongation of the asphalt satisfies the following formula As a technical feature.

[Formula 1]

148.59 ≤ AB / C < 206.75

B is the dissolution time (min) until the softening point difference in the storage stability test is measured within 2.5 占 폚, and C is the melting point measured by ASTM D113 at 5 占 폚 Means the elongation (mm).

In the above production method, the molecular weight ratio (pre-oxidation block copolymer / oxidation post block copolymer) of the vinyl aromatic hydrocarbon-conjugated diene block copolymer before oxidation to the vinyl aromatic hydrocarbon-conjugated diene block copolymer after oxidation may be 0.9 to 1.1 , Preferably 1.004 to 1.106, more preferably 1.010 to 1.103, and most preferably 1.010 to 1.100. Within this range, compatibility with the asphalt composition, shortening of the processing time, low temperature elongation and storage stability There is an effect of greatly improving.

In this case, since the vinyl 1,2 structure in the conjugated diene block is preferentially oxidized to generate an aldehyde group and a metal catalyst is not used, the thermal stability of the product can be improved by the oxidative reaction, the electric arc discharge, And excellent discoloration resistance.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as set forth in the appended claims. Variations and modifications are intended to fall within the scope of the appended claims.

[ Example ]

Example  One

≪ Preparation of block copolymer &

5,600 g of purified cyclohexane and 322 g of styrene were charged into a 20 L reactor purged with nitrogen and the temperature was raised to 50 캜 with stirring. 1.1 g of n-butyllithium was added to the mixed solution of cyclohexane and styrene at 50 DEG C to polymerize the styrene block, 717 g of butadiene was added thereto, and polymerization was continued until the butadiene completely consumed.

After the butadiene was completely consumed, 1.2 g of dichloromethylsilane was added to the reactor to conduct the coupling reaction. At this time, the chlorinated group of the dichloromethylsilane was substituted with a styrene-butadiene block in accordance with the reaction characteristics to produce a linear block copolymer.

After completion of the coupling reaction, 0.2 g of water was added to the reactor to terminate the activity of the active polymer. Thus, a linear styrene-butadiene copolymer having a weight average molecular weight of 110,311 g / mol and a styrene block content of 31% Block copolymers were prepared.

After the completion of the reaction, 7.5 g of an antioxidant Irganox 1076 (Ciba Specialty Chemicals Co.) and 15.0 g of TNPP (Weston Chemical Co.) were added to the polymerization solution to prepare a styrene-butadiene block copolymer solution.

< Functionalized  Preparation of block copolymer &gt;

600 g of the styrene-butadiene block copolymer solution was placed in a 1 L reaction vessel equipped with an external temperature jacket, set at 65 ° C, and stirred at 500 rpm. When the temperature of the reaction vessel was kept constant at 65 ° C, the voltage of the silent arc discharger connected to the 3 L reservoir (400 Torr, 100 A for controlling plasma RF power) was adjusted to 12 V. The air was introduced into the 3 L reservoir at 1 LPM, and the flow rate of the discharged air was adjusted to 1 LPM (Liter Per Minute), and the solution was poured into the stirred styrene-butadiene block copolymer solution in the reaction vessel. The gas discharged into the block copolymer solution was flowed for 10 minutes to prepare a functionalized styrene-butadiene block copolymer having a weight average molecular weight of 108,500 g / mol.

Then, a functionalized styrene-butadiene block copolymer solution was prepared by further adding 3.1 g of an antioxidant Irganox 1076 (Ciba Specialty Chemicals Co.) and 6.2 g of TNPP (Weston Chemical Co.).

<Through polymer recovery in solution Pellets  Manufacturing>

In order to recover only the polymer from the polymer solution, generally, a stripping process is performed. Namely, 3 g of Tamol and 0.5 g of CaCl 2 were added to 3 L of water and boiled.

After that, the polymer solution is slowly dropped into boiling water so that the polymer is agglomerated in water and dispersed in water in a size of 1 to 20 mm, the solvent in the solution is removed, and the polymer obtains pellets or crumbs, And dried in an oven at 60 DEG C for 12 hours to prepare a polymer pellet.

Example  2

A functionalized styrene-butadiene block copolymer (weight average molecular weight: 107,949 g / mol) was prepared in the same manner as in Example 1, except that the electric arc discharge was performed for 30 minutes in Example 1.

Example  3

A functionalized styrene-butadiene block copolymer (weight average molecular weight: 104,317 g / mol) was prepared in the same manner as in Example 1, except that the electric arc discharge was performed for 1 hour in Example 1.

Example  4

A functionalized styrene-butadiene block copolymer (weight average molecular weight: 103,188 g / mol) was prepared in the same manner as in Example 1, except that the electric arc discharge was performed for 1 hour and 30 minutes.

Example  5

A functionalized styrene-butadiene block copolymer (weight average molecular weight: 109,855 g / mol) was prepared in the same manner as in Example 1, except that the electric arc discharge was performed for 5 minutes in Example 1.

Example  6

A styrene-butadiene block copolymer (weight average molecular weight: 99,705 g / mol) was prepared in the same manner as in Example 1, except that the electric arc discharge was performed for 2 hours in Example 1.

Comparative Example  One

A styrene-butadiene block copolymer (weight average molecular weight: 110,311 g / mol) which was not functionalized was prepared by repeating the same procedure as in Example 1 except that the electric arc discharge reaction was not performed in Example 1 .

Example 7

&Lt; Preparation of asphalt composition >

500 g of AP-5 asphalt purchased from SK Innovation Co., Ltd., having physical properties shown in the following Table 1, was placed in a mixing container, and the temperature was maintained at 170 캜 and the stirring speed was 2000 rpm. Then, the functionalized 26 g of styrene-butadiene block copolymer pellets were charged.

The AP-5 had an intrinsic viscosity of 60 to 70 as measured at 25 캜 according to ASTM D946, and had physical properties shown in Table 1 below. After the functionalized styrene-butadiene block copolymer was added, the stirring speed was slowly raised to 2,500 rpm, the temperature was raised to 190 캜 and maintained for 1 hour, and the stirring was performed at a speed of 300 rpm. The resulting styrene-butadiene block copolymer was stirred until completely dissolved to prepare an asphalt composition. For reference, the functionalized styrene-butadiene block copolymer which is not dissolved initially appears white as shown in the photograph (A) of FIG. 1, but the completely dissolved styrene-butadiene block copolymer is shown in FIG. 1 B), most of the white part disappears and it becomes difficult to distinguish it from the asphalt part.

It took 10 hours for the functionalized styrene-butadiene block copolymer to completely dissolve, and the dissolved asphalt composition was sampled for physical property measurement.

asphalt Softening point
(° C) Viscosity (cps) 80 ℃ 100 ℃ 120 DEG C SK AP-5 54.1 to 55.1 22,300 4,060 1,070

Example  8

An asphalt composition was prepared in the same manner as in Example 7, except that 26 g of the functionalized styrene-butadiene block copolymer prepared in Example 2 was used.

It took 9 hours for the functionalized styrene-butadiene block copolymer to completely dissolve, and the dissolved asphalt composition was sampled for physical property measurement.

Example  9

An asphalt composition was prepared in the same manner as in Example 7 except that the functionalized styrene-butadiene block copolymer (26 g) prepared in Example 3 was used.

It took 9 hours and 10 minutes for the functionalized styrene-butadiene block copolymer to completely dissolve, and the dissolved asphalt composition was sampled for physical property measurement.

Example  10

An asphalt composition was prepared in the same manner as in Example 7 except that the functionalized styrene-butadiene block copolymer (26 g) prepared in Example 4 was used.

It took 9 hours and 50 minutes for the functionalized styrene-butadiene block copolymer to completely dissolve. The dissolved asphalt composition was sampled for physical property measurement.

Example  11

An asphalt composition was prepared in the same manner as in Example 7 except that 26 g of the functionalized styrene-butadiene block copolymer prepared in Example 5 was used.

It took 10 hours and 50 minutes for the functionalized styrene-butadiene block copolymer to completely dissolve, and the dissolved asphalt composition was sampled for physical property measurement.

Example  12

An asphalt composition was prepared in the same manner as in Example 7, except that 26 g of the functionalized styrene-butadiene block copolymer prepared in Example 6 was used.

It took 10 hours and 40 minutes for the functionalized styrene-butadiene block copolymer to completely dissolve, and the dissolved asphalt composition was sampled for physical property measurement.

Comparative Example  2

An asphalt composition was prepared in the same manner as in Example 7 except that the non-functionalized styrene-butadiene block copolymer (26 g) prepared in Comparative Example 1 was used.

It took 11 hours for the functionalized styrene-butadiene block copolymer to completely dissolve, and the dissolved asphalt composition was sampled for physical property measurement.

[Test Example]

Properties of the styrene-butadiene block copolymer or the asphalt composition prepared in Examples 1 to 12 and Comparative Examples 1 and 2 were measured by the following methods and the results are shown in Tables 2 to 3 and 2 to 4 It was

* Softening point - Determined according to ASTM36.

* Elongation - The specimen is left for 1 hour at 5 ° C and measured according to ASTM D 113.

* Dissolution time - The dissolution time until the difference in softening point was measured within 2.5 ° C in the storage stability test was first dissolved by microscope until no particles were observed, and after the storage stability test, the time (min) was measured.

* Storage Stability - AASHTO (American Association of State Highway and Transportation Officials) A method of measuring the softening point by the method of PP5 and measuring the softening point according to the ASTM D36 method. More specifically, 50 g of an asphalt composition is refined in an aluminum tube, After standing for 48 hours in the oven, take out the third part, measure the softening point of the upper part and the lower part, and measure the temperature difference. The smaller the temperature difference is, the better the storage stability is, and it is said that phase separation does not occur when the temperature difference is usually within 2.5 ° C.

* Aldehyde content ( ppm ) - Each sample was dissolved in 1,1,2,2-tetrachloroethane-D2 and loaded on 500 MHz 1 H NMR (manufacturer Varian, Model: VNMRS500) peak), the content of each aldehyde group was determined using the following formula (2).

[Formula 2]

The number of hydrogen atoms in the aldehyde group = (aldehyde group content ppm x block copolymer molecular weight (-> 110,000 g / mol) / 1,000,000 / 56 g / mol (molecular weight of -> - CH - CH (CHO) -).

* Content of vinyl group (-CH-CH-CH = CH2) - Each sample was dissolved in 1,1,2,2-tetrachloroethane-D2 and analyzed by 500 MHz 1 H NMR (Varian, Model: VNMRS500 ), And then the respective vinyl group contents were determined from the values obtained from the peaks near 5.2 ppm.

* Weight average molecular weight (g / mol ) - Each sample was dissolved in THF for 30 minutes, loaded on GPC and flowed, and the molecular weight was compared with the standard molecular weight of the PS standard.

Copolymer Electric arc discharge time Content of aldehyde group (ppm) Average number of aldehyde groups ^{1 )} Weight average molecular weight (g / mol) Molecular weight ratio ²⁾ Example 1 10 minutes 412 0.81 108,500 1.017 Example 2 30 minutes 801 1.57 107,949 1.022 Example 3 60 minutes 1266 2.49 104,317 1.057 Example 4 1 hour 30 minutes 1511 2.97 103,188 1.069 Example 5 5 minutes 40 0.08 109,855 1.004 Example 6 2 hours 1764 3.47 99,705 1.106 Comparative Example 1 0 minutes 0 0 110, 311 1,000

¹⁾ is the average number of functionalized aldehydes per ¹ 000 g / mol weight-average molecular weight of the block copolymer (measured by ¹ H NMR spectrometry in ^1, 1,2,2-tetrachloroethane-D2 dissolved at 500 MHz) , ²⁾ is a value obtained by dividing the weight-average molecular weight of Comparative Example 1 by the weight-average molecular weight of each of the Examples.

As shown in Table 2, it was confirmed that the content of the aldehyde group (aldehyde structure) and the number of aldehyde groups were increased as the arc discharge treatment time was increased. In the case of Examples 1 to 4, the ratio of molecular weight (= molecular weight before oxidation / molecular weight after oxidation) was formed to be 1.010-1.100, and the weight average molecular weight There is no big difference.

However, in Example 6 where the arc discharge treatment time was 2 hours, the molecular weight ratio was 1.106 and the molecular weight after oxidation was further reduced. In Example 5 where the arc discharge treatment time was short, the molecular weight ratio was 1.004, Respectively.

The properties of the asphalt composition and the dissolution time through phase separation data were compared with each other in Examples 1 to 6 and Comparative Example 1 in Table 2 as shown in Table 3 (physical properties and dissolution time of the asphalt composition).

Asphalt composition Asphalt dissolution time ³⁾ : B Softening point
(° C): A Shindo
(mm, 5 캜): C Shindo
(mm, 15 ° C) Storage stability
( ? C) ⁴⁾ Equation 1 (AB / C *) Example 7 10 hours 63.5 201.5 755.5 0.4 189 Example 8 9 hours 62.3 213.5 759 0.5 157.57 Example 9 9 hours 10 minutes 61.6 228 765 1.7 148.59 Example 10 9 hours 50 minutes 62.1 235 793 0.7 155.91 Example 11 10 hours and 50 minutes 62.5 196.5 757 1.0 206.74 Example 12 10 hours and 40 minutes 59.7 192 748.5 1.3 199 Comparative Example 2 11 hours 63.9 195 753.5 0.8 216

³⁾ was sampled in accordance with AASHTO PP5 method and the softening point was measured by ASTM D36 method. The difference in melting time was within 2.5 ℃, and ⁴ ) the difference in softening point (℃).

As shown in Table 3 above, the asphalt compositions (Examples 7 to 12) comprising the functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer of the present invention were prepared by mixing the non-functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer (Comparative Example 2), the dissolution rate was remarkably shortened, and the elongation and storage stability were excellent. Particularly, in Examples 7 to 10, the dissolution rate was remarkably shortened , Elongation and storage stability were also significantly improved.

Figure 2 is a spectrum according to the ¹ H NMR spectrum of Comparative Example 1 in ¹ H NMR spectrum of the block copolymer that is not subjected to oxidation treatment as in Example 6, the aldehyde is functionalized production block for 2 hours, the copolymer in the functionalized processing degree It is a table in which the pair of spectra overlapped to see the change and the change amount of the major ¹ H NMR peak of these.

As a result, 1H of aldehyde was observed between 9.6 and 9.9 ppm, and it was confirmed that the block copolymer was functionalized by the arc discharge method.

Claims (16)

A vinyl aromatic hydrocarbon-conjugated diene block copolymer added to asphalt, wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer contains a 1,4 structure, a vinyl 1,2 structure, and an aldehyde structure in a butadiene block, and the aldehyde Structure comprises a partial oxidation of the vinyl 1,2 structure by an oxidative reaction or an electrical acrylic discharge to within the range of 40 to 1740 ppm,
The vinyl aromatic hydrocarbon vinyl-conjugated diene block copolymer has a molecular weight ratio (before oxidation block copolymer / oxidation post block copolymer) of 1.004-1.106 before and after oxidation,
Wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer is added to the asphalt so that the dissolution time, softening point and elongation of the asphalt satisfy the following formula:
[Formula 1]
148.59 &amp;le; AB / C &lt; 206.75
B is the dissolution time (min) until the softening point difference in the storage stability test is measured within 2.5 占 폚, and C is the melting point measured by ASTM D113 at 5 占 폚 (Mm). delete delete The method according to claim 1,
Wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer has a weight average molecular weight of 80,000 to 3,000,000 g / mol. The method according to claim 1,
The vinyl aromatic hydrocarbons may be selected from the group consisting of styrene, alpha-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4- cyclohexylstyrene, 4- (para- -5-hexynaphthalene. &Lt; / RTI &gt; The method according to claim 1,
The butadiene block may be selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, &Lt; / RTI &gt; wherein the modifier is provided by at least one conjugated diene selected from the group consisting of ethylene and propylene. The method according to claim 1,
Wherein the vinyl aromatic hydrocarbon and the conjugated diene have a weight ratio of 5:95 to 40:60. The method according to claim 1,
The vinyl aromatic hydrocarbon-conjugated diene block copolymer is represented by the following general formula (1)
[Chemical Formula 1]

(Wherein A to D are independently CH ₂ -CH = CH-CH or CH ₂ -CH when the butadiene is used as the conjugated diene (provided that all of A to D are CH ₂ -CH = CH-CH, may be CH ₂ -CH is one of N), W ~ Z is a, B, C or H when D is a CH ₂ -CH = CH-CH, a vinyl group, or an aldehyde group when the CH ₂ -CH, D, e, f, and g represent the number ratio of 1,4 structure, vinyl 1,2 structure and aldehyde structure, the 1,4 structure is 605,622 to 606,796 ppm, and the vinyl 1,2 structure is 76,608 To 77,269 ppm, the aldehyde structure is 40 to 1,764 ppm, G is a vinyl aromatic hydrocarbon, p is an integer number ratio of vinyl aromatic hydrocarbons to A, B, C and D, and the vinyl aromatic hydrocarbon and the conjugated diene Is in the range of 5:95 to 40:60 and F is a vinyl aromatic hydrocarbon block, H, CH ₂ CHO, CH ₂ COOH or a coupling group, and either WZ or F One having an aldehyde group, q being 1 to 10 as the number of arms centered on F, said coupling group being a group derived from a coupling agent, The method according to claim 1,
Wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer is composed of a triblock copolymer and a diblock copolymer. 10. The method of claim 9,
Wherein the triblock copolymer is 40 wt% to less than 100 wt%, and the diblock copolymer is more than 0 wt% to 60 wt%.
The method according to claim 1,
Wherein the vinyl aromatic hydrocarbon-conjugated diene block copolymer is modified by using a coupling agent coupled to the vinyl aromatic hydrocarbon-conjugated diene block copolymer. The method according to claim 1,
Wherein the asphalt modifier has a peak in the range of 9.6 to 9.9 ppm in nuclear magnetic resonance (NMR) analysis.
An asphalt composition comprising the polymer modifier for asphalt of claim 1.
14. The method of claim 13,
Wherein the asphalt composition comprises asphaltenes.
14. The method of claim 13,
Wherein the asphalt composition has a weight mixing ratio of the modifier to the asphalt of 0.1: 99.1 to 20:80. delete

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