KR102207520B1 - Asphalt modifier and modified asphalt composition comprising the same - Google Patents

Abstract

The present invention relates to an asphalt modifier and an asphalt composition comprising the same, and more particularly, when a vinyl aromatic hydrocarbon-conjugated diene block copolymer containing a specific polyfunctional functional group is used as an asphalt modifier, it has excellent compatibility with the asphalt composition. It relates to an asphalt modifier for effectively improving the storage stability of the asphalt composition and an asphalt composition comprising the same.

Description

Asphalt modifier and modified asphalt composition comprising the same TECHNICAL FIELD [0002] Asphalt modifier and modified asphalt composition comprising the same

The present invention relates to an asphalt modifier having excellent compatibility with asphalt and a modified 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 has properties that become hard at temperatures below room temperature.

Asphalt is widely applied to building materials such as road pavement and waterproofing because it has rich plasticity, high waterproof, electrical insulation, adhesion, and chemically stable characteristics. However, when asphalt is 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.

Specifically, vinyl aromatic 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 a vinyl aromatic hydrocarbon-conjugated diene block copolymer is used as an asphalt modifier, a lot of time and cost are required for dissolution at high temperature. Therefore, the most important physical property of the block copolymer used as an asphalt modifier is compatibility with the asphalt composition.

However, the content of asphaltene, a by-product of oil refining, is increasing as oil refineries continue to be upgraded due to the recent increase in crude oil prices and energy saving policies. Asphaltene is an aggregate of aromatic hydrocarbons, since it contains a large number of polar functional groups at the ends, it has poor compatibility with a block copolymer without polar functional groups. This not only greatly prolongs the processing time or manufacturing time of the asphalt, but also causes degradation of the quality of the asphalt such as lowering the elasticity of the modified asphalt.

Therefore, in order to increase compatibility with the asphalt composition, various studies such as adjusting the molecular weight of the SBS block copolymer or changing the microstructure of the block copolymer to add a coupling effect or adding an additive such as oil as a processing aid. Is in progress.

For example, Korean Patent Application Publication No. 2016-0052310 uses a vinyl aromatic hydrocarbon-conjugated diene block copolymer containing a heterogeneous conjugated diene block having a peak molecular weight (Mp) in a specific content as an asphalt modifier, and is compatible with an asphalt composition. It is disclosed that the properties and physical properties of asphalt can be improved.

In addition, Korean Patent Application Publication No. 2015-0102869 uses a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer in which an aldehyde group is bonded to the main chain of the conjugated diene block as an asphalt modifier. And it discloses that the storage stability can be improved.

These patents have improved the compatibility with the asphalt composition to some extent, but the effect is not sufficient. In addition, since the quality deviation of each asphalt according to crude oil is large, and the resulting modification effect is also different, it is not an ultimate solution. Accordingly, research on a vinyl aromatic hydrocarbon-conjugated diene block copolymer as an asphalt modifier having excellent compatibility with an asphalt composition and excellent modifying performance is required.

Republic of Korea Patent Publication No. 2016-0052310 (2016.05.12), asphalt modifier and asphalt composition containing the same Republic of Korea Patent Publication No. 2015-0102869 (2015.09.08), a functionalized vinyl aromatic hydrocarbon-conjugated diene block copolymer composition, a method for producing the same, and an asphalt composition comprising the same

Accordingly, the present inventors conducted various studies to solve the above problems, and as a result of using an asphalt modifier containing a vinyl aromatic hydrocarbon-conjugated diene block copolymer into which a specific polyfunctional functional group was introduced, it was compatible with the asphalt composition. It was confirmed that the improvement of the property can increase the reforming effect of asphalt.

Accordingly, an object of the present invention is to provide an asphalt modifier that can effectively improve dissolution properties for an asphalt composition.

In addition, another object of the present invention is to provide a method for producing the asphalt modifier.

In addition, another object of the present invention is to provide a modified asphalt composition comprising the asphalt modifier.

In order to achieve the above object, the present invention is represented by the following formula (1), comprising a vinyl aromatic hydrocarbon-conjugated diene block copolymer backbone, and bonded to the vinyl aromatic hydrocarbon-conjugated diene block copolymer backbone, represented by formula (2) Asphalt modifiers containing polyfunctional functional groups are provided:

[Formula 1]

[Formula 2]

(In Formulas 1 and 2, A, B, C, X, m, n, o, p, R ₁ and R ₂ follow the descriptions in the specification.)

In addition, the present invention comprises the steps of producing a vinyl aromatic hydrocarbon block by carrying out a polymerization reaction of a vinyl aromatic hydrocarbon-based monomer in a hydrocarbon-based solvent using a polymerization initiator;

Mixing the vinyl aromatic hydrocarbon block, a polymerization initiator, and a conjugated diene monomer and performing a polymerization reaction to prepare a vinyl aromatic hydrocarbon-conjugated diene block copolymer; And

It provides a method for producing the asphalt modifier comprising; mixing the vinyl aromatic hydrocarbon-conjugated diene block copolymer and a coupling agent to couple a polyfunctional functional group.

The coupling agent is ethyl (methyl) carbam chloride, dimethyl carbam chloride, diethyl carbam chloride, N,N-diisopropylcarbam chloride, methyl (phenyl) carbam chloride, diphenylcarbam chloride, benzyl ( Methyl)carbam chloride, 4-morpholinecarbonyl chloride, 4-methyl-1-piperazinecarbonyl chloride, 1-piperidinecarbonyl chloride, 1-pyrrolidinecarbonyl chloride and 4-methyl-1- It is characterized in that it contains at least one selected from the group consisting of piperazinecarbonyl chloride.

In addition, the present invention provides an asphalt composition comprising an asphalt, a crosslinking agent and the asphalt modifier.

The asphalt modifier according to the present invention has excellent compatibility with asphalt by introducing a specific polyfunctional functional group into the vinyl aromatic hydrocarbon-conjugated diene block copolymer, and by using it in the asphalt composition, workability is greatly improved as well as the high temperature properties of asphalt. Storage stability can be effectively modified while maintaining silver.

Hereinafter, the present invention will be described in more detail.

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

In order to improve the physical properties of the asphalt composition, a vinyl aromatic hydrocarbon-conjugated diene block copolymer is used as an asphalt modifier.

The asphalt composition is largely composed of four components, and among them, asphaltene is the component that has the worst compatibility with the vinyl aromatic hydrocarbon-conjugated diene block copolymer, which is an asphalt modifier. Asphaltene is chemically a highly concentrated aromatic hydrocarbon compound with polar functional groups with many heteroatoms. However, since the vinyl aromatic hydrocarbon-conjugated diene block copolymer used as an asphalt modifier does not have a polar functional group, it is not compatible with the asphalt composition, and thus processability and workability are deteriorated, and the asphalt modifier is not sufficiently mixed with the asphalt composition. It causes the quality of asphalt to deteriorate such as lowering of elasticity.

To improve this, a method of changing the composition or molecular weight range of the block copolymer or adding a hydrophilic monomer, oil, etc. to the asphalt composition was used, but chain breakage of the block copolymer occurred, resulting in a decrease in molecular weight and thus the asphalt composition. There is a problem that the physical properties of the material are rather deteriorated.

Accordingly, the present invention proposes an asphalt modifier comprising a vinyl aromatic hydrocarbon-conjugated diene block copolymer into which a specific polyfunctional functional group is introduced that can ensure excellent compatibility when incorporated into an asphalt composition.

Specifically, the asphalt modifier according to the present invention includes a vinyl aromatic hydrocarbon-conjugated diene block copolymer main chain and a polyfunctional functional group bonded thereto, and may be represented by the following Formula 1:

[Formula 1]

(In Formula 1,

A to C blocks are independently of each other a vinyl aromatic hydrocarbon block or a conjugated diene block, X is a polyfunctional functional group represented by the following formula (2), m, n, and o are integers of 0 or more, and m+n+o is 2 or more. And p is an integer of 0<p≤3.)

[Formula 2]

(In Chemical Formula 2,

R ₁ and R ₂ are the same as or different from each other, and each independently selected from a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a C3 to C20 cycloalkyl group, or a C6 to C20 aryl group;

Or the R ₁ and R ₂ may be connected to each other to form an aliphatic ring or an aromatic ring, and at least one of the carbon atoms constituting the aliphatic ring or aromatic ring is nitrogen (N), oxygen (O), sulfur (S) And phosphorus (P) may be substituted with one or more hetero atoms selected from the group consisting of,

* Is a part that can be combined with a vinyl aromatic hydrocarbon block or a conjugated diene block unit in a vinyl aromatic hydrocarbon-conjugated diene block copolymer among the polyfunctional functional groups, and at this time, a vinyl aromatic hydrocarbon-conjugated diene block copolymer 1 per molecule of the polyfunctional functional group Molecules can be bound.)

The term "alkyl group" used in the present invention may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20, specifically 1 to 10. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a heptyl group, but are not limited thereto.

The term "alkoxy group" as used herein refers to an alkyl group having 1 to 20 carbon atoms having an oxygen atom through an ether bond at the end of the carbon chain, unless otherwise specified, and is not limited thereto.

The term “cycloalkyl group” or “aliphatic ring” as used in the present invention means a non-aromatic carbon-based ring consisting of at least 3 carbon atoms. For example, there are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like, but are not limited thereto.

The term "aryl group" or "aromatic ring" as used herein refers to a single or multiple aromatic carbon-based ring having 6 to 20 carbon atoms. For example, there may be a phenyl group, a biphenyl group, a fluorene group, and the like, but is not limited thereto.

The vinyl aromatic hydrocarbon block is a polymer unit consisting of a vinyl-containing C6 to C30 aromatic hydrocarbon compound such as styrene, vinyl naphthalene, vinyl toluene or vinyl xylene as a monomer. Preferably, the vinyl aromatic hydrocarbon block may be a polystyrene block including a structure derived from a styrene-based compound. For example, the vinyl aromatic hydrocarbon block is styrene; C1 to C20 alkyl) styrene such as alpha (α)-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, and the like; C3 to C30 cycloalkyl) styrene such as 4-cyclohexylstyrene; It may include at least one selected from the group consisting of C6 to C30 aryl styrene and C7 to C30 aralkyl styrene, such as 4-(para-methylphenyl)styrene.

The weight average molecular weight (M _w ) of the vinyl aromatic hydrocarbon block may be 3,000 to 35,000 g/mol, preferably 10,000 to 25,000 g/mol. When the vinyl aromatic hydrocarbon block falls within the above range, it is possible to improve low temperature properties while maintaining high temperature properties and storage stability of asphalt.

The conjugated diene block is a diolefin having a pair of conjugated double bonds, and may include a structure derived from a butadiene-based compound. For example, the conjugated diene block is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-butyl-1,3-octadiene, 2-methyl-1,3-butadiene, 1, It may include at least one selected from the group consisting of 3-pentadiene, 1,3-hexadiene, and 2-phenyl-1,3-butadiene.

The weight average molecular weight of the conjugated diene block may be 10,000 to 150,000 g/mol, preferably 20,000 to 100,000 g/mol. When the weight average molecular weight of the conjugated diene block is less than the above range, it may not be easy to express mechanical properties of the block copolymer. Conversely, when it exceeds the above range, a problem of deteriorating processability may occur.

More preferably, as the vinyl aromatic hydrocarbon, styrene or alpha-methylstyrene, 3-methylstyrene, and 4-methylstyrene may be used alone or in combination, and as the conjugated diene, butadiene or 2-methyl-1,3-butadiene Can be used alone or in combination.

In this case, the weight ratio of the vinyl aromatic hydrocarbon block and the conjugated diene block may be 1:1 to 1:4. When the weight ratio falls within the above range, it is stably dissolved in the modified asphalt composition to obtain a sufficient modification effect. If the content of the vinyl aromatic hydrocarbon is less than the above range, it is difficult for the vinyl aromatic hydrocarbon block to achieve a physical crosslinking point, so that the physical properties of asphalt are deteriorated. .

The block copolymer represented by the [ABC] block is linear, branched, symmetric, asymmetric, or radial styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), or styrene-butadiene (SB) A double block copolymer may be used, and two or more of them may be used in combination, and it is more preferable to use styrene-butadiene-styrene (SBS).

In addition, the block copolymer represented by the [A-B-C] block may have a weight average molecular weight of 15,000 to 500,000 g/mol, preferably 17,000 to 300,000 g/mol, and may be linear or branched or a mixture thereof. When the molecular weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer is less than the above range, the molecular weight of the vinyl aromatic hydrocarbon block is too small to lower the high-temperature properties. Conversely, when it exceeds the above range, the solubility in asphalt is remarkable. Falls out.

In particular, the asphalt modifier according to the present invention includes a polyfunctional functional group X represented by Chemical Formula 2 in the main chain of the vinyl aromatic hydrocarbon-conjugated diene block copolymer in order to further improve compatibility and solubility with respect to asphalt.

The polyfunctional functional group X is derived from a coupling agent, and specifically, a vinyl aromatic hydrocarbon that can be used as a coupling agent and an asphalt modifier in the presence of a living anion or an organometallic compound, a polymer chain having an anionic end initiated from a polymerization initiator. -It can be formed by reaction between conjugated diene block copolymers. In particular, the asphalt modifier of the present invention exhibits polarity by introducing the polyfunctional functional group X represented by Formula 2 into the main chain of the vinyl aromatic hydrocarbon-conjugated diene block copolymer, so that the asphalt modifier is sufficiently dissolved in the asphalt composition at a rapid rate, It serves to increase the compatibility of the product. Accordingly, since the asphalt modifier is uniformly kneaded in the asphalt composition, the effect of improving physical properties of the asphalt composition according to the addition of the asphalt modifier can be sufficiently obtained.

The multifunctional functional group X is represented by Formula 2, and R ₁ and R ₂ in Formula 2 are the same as or different from each other as described above, and each independently a C1 to C20 alkyl group, a C1 to C20 alkoxy group, and C3 to C20 It is selected from a cycloalkyl group or a C6 to C20 aryl group; Or the R ₁ and R ₂ are linked to each other to be a 5- or 6-ring aliphatic or aromatic ring. Preferably, R ₁ and R ₂ are each a C1 to C4 alkyl group, a C3 to C7 cycloalkyl group, or a C6 to C12 aryl group, or are connected to each other to form a piperidine group, piperazine group, pyrrolidine group, or morpholine. It can be a flag.

Since the polyfunctional functional group X includes a tertiary amine group and a hydroxy group representing polarity, compatibility and solubility may be improved by increasing reactivity with the polar group of asphalt. Specifically, compared to the conventional dichlorodimethylsilane used as a coupling agent containing only two methyl groups, the present invention introduces a tertiary amine group and a hydroxy group to the asphalt modifier using the coupling agent containing the polyfunctional functional group X. Accordingly, it exhibits high reactivity with the polar group of asphalt, so that it can have excellent compatibility with asphalt. This improvement in compatibility also leads to an increase in solubility. At this time, the solubility property can be confirmed through a phase separation test, and it can be confirmed that it has superior solubility compared to that of using an asphalt modifier in which a functional group is introduced with dichlorodimethylsilane based on Table 1 described below.

In the asphalt modifier of the present invention, the content of the polyfunctional functional group X may be 40 to 4700 ppm, preferably 100 to 3500 ppm, based on the total weight 1 of the vinyl aromatic hydrocarbon-conjugated diene block copolymer. If it falls within the above range, compatibility with asphalt may be increased, and physical properties such as a use temperature range and lifespan of asphalt including the same may be improved.

In addition, the present invention provides a method for producing the above-described asphalt modifier.

The method for preparing an asphalt modifier according to the present invention comprises: preparing a vinyl aromatic hydrocarbon block through a polymerization reaction using a polymerization initiator in a hydrocarbon-based solvent; Mixing the vinyl aromatic hydrocarbon block, a polymerization initiator, and a conjugated diene monomer and performing a polymerization reaction to prepare a vinyl aromatic hydrocarbon-conjugated diene block copolymer; And coupling a polyfunctional functional group by mixing the vinyl aromatic hydrocarbon-conjugated diene block copolymer and a coupling agent.

It will be described in detail for each step below.

First, a vinyl aromatic hydrocarbon block is prepared through a polymerization reaction using a polymerization initiator in a hydrocarbon-based solvent.

As described above, the vinyl aromatic hydrocarbon-based monomer may include a vinyl group-containing C6 to C30 aromatic hydrocarbon-based compound. The vinyl aromatic hydrocarbon-based monomer may be used in an appropriate amount in consideration of the content of the vinyl aromatic hydrocarbon block in the finally produced vinyl aromatic hydrocarbon-conjugated diene block copolymer.

The hydrocarbon-based solvent does not react with a polymerization initiator to be described later, and can be used without particular limitation as long as it is usually used for polymerization reaction. For example, the hydrocarbon-based solvent may be a linear or branched hydrocarbon compound 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 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 further include a polar solvent to control the vinyl content and improve the polymerization rate during polymerization of the conjugated diene monomer. For example, the polar solvent may include at least one selected from the group consisting of tetrahydrofuran, ethyl ether, etramethylethylene diamine, and benzofuran.

In general, the polymerization initiator may be used without any particular limitation that can be used for anionic polymerization.

The polymerization initiator may be an organometallic compound or a living anion, which is a polymer chain having an anionic end initiated from the polymerization initiator.

The organometallic compound may be an organolithium compound of Formula 3:

[Formula 3]

(In Chemical Formula 3,

R ₃ is a C1 to C20 aliphatic, aromatic or alkyl substituted aromatic hydrocarbon group.)

The term "aliphatic hydrocarbon group" as used herein refers to a group having a carbon skeleton without including an aromatic ring as a relative concept to aromatics.

For example, the organometallic compound is n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allyllithium, vinyllithium, phenyllithium and benzyllithium. It may include one or more selected from the group consisting of.

Subsequently, the vinyl aromatic hydrocarbon block, a polymerization initiator, and a conjugated diene monomer are mixed and a polymerization reaction is performed to prepare a vinyl aromatic hydrocarbon-conjugated diene block copolymer.

As described above, the conjugated diene monomer may be a butadiene-based compound. The conjugated diene monomer may be used in an appropriate amount in consideration of the content of the conjugated diene block in the final produced vinyl aromatic hydrocarbon-conjugated diene block copolymer.

The polymerization reaction of the conjugated diene may also be carried out by anionic polymerization reaction as in the above-described step. Therefore, the polymerization initiator is as described above.

In the polymerization reaction over the above two steps, the polymerization initiator may be included in an amount of 0.3 to 3.3 mmol based on the total content of the vinyl aromatic hydrocarbon-conjugated diene block copolymer. If the content of the polymerization initiator is less than the above range, it may be difficult to introduce a multifunctional functional group because the reaction with the coupling agent described later is difficult due to a very high molecular weight and low reactor stirring efficiency, and on the contrary, when it exceeds the above range There is a disadvantage that productivity may be seriously deteriorated in the post-treatment process.

The polymerization reaction is preferably carried out until the consumption rate of the conjugated diene monomer is 99% or more 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.

In addition, a vinyl aromatic hydrocarbon-conjugated diene block copolymer in which the above-described vinyl aromatic hydrocarbon block and conjugated diene block are cross-arranged is prepared through the polymerization reaction, wherein at least one block of the A to C blocks in Formula 1 It is preferred to include an aromatic hydrocarbon block.

Subsequently, the vinyl aromatic hydrocarbon-conjugated diene block copolymer and a coupling agent are mixed to couple a polyfunctional functional group to the vinyl aromatic hydrocarbon-conjugated diene block copolymer.

In the coupling reaction, X, which is a polyfunctional functional group represented by Formula 2, is introduced into the main chain of the vinyl aromatic hydrocarbon-conjugated diene block copolymer represented by Formula 1, and at the same time, conjugated diene blocks between the block copolymers are connected.

The coupling agent is not particularly limited as long as it is a compound including the multifunctional functional group X represented by Formula 2, but may be a compound including a carbamoyl structure represented by Formula 4:

[Formula 4]

(In Chemical Formula 4,

R ₁ and R ₂ are as mentioned above, and Y is a halogen element.)

The halogen element is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I), preferably chlorine.

Specifically, the coupling agent is ethyl (methyl) carbamic chloride (ethyl (methyl) carbamic chloride), dimethyl carbamic chloride (dimethylcarbamic chloride), diethylcarbamic chloride (diethylcarbamic chloride), N,N-diisopropylcar Chestnut chloride (N,N-diisopropylcarbamic chloride), methyl (phenyl) carbamic chloride, diphenylcarbamic chloride, benzyl (methyl) carbamic chloride chloride), 4-morpholinecarbonyl chloride, 4-methyl-1-piperazinecarbonyl chloride, 1-piperidinecarbonyl chloride (1- piperidinecarbonyl chloride), 1-pyrrolidinecarbonyl chloride, 4-methyl-1-piperazinecarbonyl chloride, and at least one selected from the group consisting of can do. Preferably, the coupling agent is ethyl (methyl) carbam chloride, dimethyl carbam chloride, methyl (phenyl) carbamic chloride (methyl (phenyl) carbamic chloride), 4-morpholinecarbonyl chloride (4-morpholinecarbonyl chloride) and It may be one or more selected from the group consisting of 4-methyl-1-piperazinecarbonyl chloride.

The coupling agent may react with an anionic active site at the block end of the vinyl aromatic hydrocarbon-conjugated diene block copolymer prepared through the above-described process to link between the conjugated diene blocks between the block copolymers and perform a functionalization reaction. .

Through the coupling reaction as described above, the vinyl aromatic hydrocarbon-conjugated diene block copolymer of Formula 1 is prepared. At this time, in the product obtained as a result of the coupling reaction, a vinyl aromatic hydrocarbon-conjugated diene block copolymer not subjected to a coupling reaction may be mixed and present.

In addition, the present invention provides a modified asphalt composition comprising asphalt, a crosslinking agent and the above-described asphalt modifier.

The asphalt is a residue obtained by refining crude oil, mainly composed of hydrogen and carbon, and composed of a hydrocarbon compound in which a small amount of nitrogen, sulfur or oxygen is bound. The asphalt is conventional and includes both natural and petroleum asphalt, and is not particularly limited. For example, the asphalt is natural asphalt (buton natural asphalt), straight asphalt (stright asphalt), blown asphalt (blown asphalt), goose asphalt (guss asphalt), cutback asphalt (cutback asphalt), emulsified asphalt, sebum (PG) ) Grade asphalt, and the like, and preferably straight asphalt.

The straight asphalt is a final residue obtained by distilling crude oil from an atmospheric pressure distillation column under reduced pressure again, and contains a lot of bitumen that is not decomposed, and can be used as a raw material for various petroleum-based asphalt. The straight asphalt may be manufactured directly or commercially available products through a method commonly performed in the art. Commercially available straight asphalt includes AP-3 and AP-5 provided by SK Energy or GS Caltex.

The asphalt may contain 1 to 40%, specifically 5 to 30% of asphaltene in the total content.

The asphalt modifier is for improving compatibility with asphalt and follows the above description.

The crosslinking agent serves to improve the compatibility of the above-described asphalt modifier with asphalt. The crosslinking agent is not particularly limited as long as it is a sulfur compound containing sulfur or iron sulfate, and a representative example thereof is elemental sulfur.

For example, the modified asphalt composition presented in the present invention may include 1 to 10 parts by weight of an asphalt modifier, 87 to 98.95 parts by weight of an asphalt, and 0 to 3 parts by weight of a crosslinking agent.

It is possible to secure excellent storage stability of the asphalt composition within the above range. If the content of the asphalt modifier exceeds the above range, the production cost of the modified asphalt composition increases, and when the content of the crosslinker exceeds the above range, the modified asphalt loses elasticity due to excessive crosslinking reaction and gelation ( gelation). On the other hand, when the content of each of the asphalt modifier and the crosslinking agent is less than the above range, the degree of asphalt modification is low, so that high temperature properties and elasticity of the modified asphalt are deteriorated.

In addition, the asphalt modifier, crosslinking agent, and asphalt of Formula 1 are mixed with asphalt using a high-speed shear mixer and a low-shear mixer to obtain a modified asphalt composition according to the present invention.

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

When the asphalt composition contains about 4 to 5% by weight of the modifier under vulcanization conditions, the melting rate is preferably 1 to 10 hours, and more preferably 1 to 8 hours based on this. That is, within this range, there is an effect of excellent balance of physical properties of the asphalt composition.

As an example, the blending process of the modified asphalt composition is as follows. Put the asphalt in a 1L container and keep the asphalt at a temperature of 150 to 170°C, preferably 160 to 165°C for 30 minutes to 2 hours, preferably for 40 minutes or longer to sufficiently molten the asphalt modifier of the above formula 1 into the asphalt. Add while gradually increasing the stirring speed. At this time, the speed of the high-speed shear mixer is maintained at 2,500 rpm and stirred for 1 hour while adjusting to 180 to 195 °C, preferably 190 °C. Thereafter, it was transferred to an impeller-type stirrer and maintained at 250 rpm at the same temperature, stirred for an additional 4 hours or more, preferably 5 to 8 hours, and the modified asphalt composition was sampled at regular intervals to measure physical properties. At this time, the modified asphalt composition is sampled at regular intervals to measure physical properties. Specifically, the modified asphalt composition was sampled in an aluminum tube for each mixing time and stored in an oven at 180° C. for a certain period of time, and the solubility was confirmed by the difference in softening points between the upper and lower layers of the aluminum tube.

The modified asphalt composition of the present invention may have a softening point of 65° C. and a viscosity range of 3,000 cPs or less. In this case, the viscosity is not limited to any specific range, and the viscosity may be preferably as small as 3,000 cPs or less. For example, the viscosity may be in the range of 300 to 3,000 cPs, but is not limited thereto.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

Example 1: asphalt Modifier And asphalt composition preparation

(1) asphalt Modifier Produce

4,287 g of purified cyclohexane and 273 g of styrene were added to a 10 liter reactor substituted with nitrogen, and the temperature was raised to 60°C while stirring. 1.15 g of n-butyllithium was added to the mixed solution of cyclohexane and styrene at 60° C. to polymerize a styrene block, and then 607.5 g of butadiene was added thereto, followed by polymerization until the butadiene was completely consumed.

After completion of the polymerization reaction, 1.12 g of 4-morpholinecarbonyl chloride was added as a coupling agent to perform a coupling reaction.

Subsequently, after adding 0.2 g of water as a reaction terminator to remove the reaction activity, 6.16 g of a solution of a mixture of the primary antioxidant and the secondary antioxidant, which is an antioxidant, was added to the polymerization solution to obtain a weight average molecular weight of about 110. A linear styrene-butadiene block copolymer in kg/mol and a styrene block content of 31% by weight was prepared.

At this time, the weight average molecular weight is determined by dissolving each polymer pellet sample in tetrahydrofuran (THF) for 30 minutes, loading it on GPC (Gel permeation chromatography, waters) and flowing, and then comparing it with the standard molecular weight of the PS (polystyrene) standard. The molecular weight was measured.

Subsequently, in order to recover only the block copolymer from the reaction solution, a stripping process was generally 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, and then the solution containing the block copolymer was slowly added to slowly boiling water to aggregate the block copolymer in water. . The agglomerated block copolymer was dried in an oven at 60° C. for 16 hours to prepare styrene-butadiene block copolymer pellets.

(2) Preparation of asphalt composition

500 g of asphalt (AP-5, SK) was put in a mixing container (heating mantle), and each asphalt modifier prepared in the above Examples and Comparative Examples was added to each asphalt composition while stirring at a high shear rate of 2,500 rpm at 190°C. It was added in an amount of 4.5% by weight based on the total weight.

Then, after 1 hour, the mixture was stirred at a low shear rate of 250 rpm. At this time, an asphalt composition was prepared by stirring for 4 hours while observing with a fluorescence microscope.

Example 2: asphalt Modifier And asphalt composition preparation

Weight average molecular weight in the same manner as in Example 1, except that 1.04 g of 4-methyl-1-piperazinecarbonyl chloride was used instead of using 4-morpholinecarbonyl chloride, which is the coupling agent of Example 1. Styrene-butadiene block copolymer pellets of about 110 kg/mol and a styrene block content of 31% by weight were prepared.

Subsequently, an asphalt composition was prepared in the same manner as in Example 1.

Example 3: asphalt Modifier And asphalt composition preparation

The weight average molecular weight was about 110 kg/mol in the same manner as in Example 1, except that 0.79 g of dimethylcarbam chloride was used instead of the coupling agent of Example 1, 4-morpholinecarbonyl chloride. , A styrene block content of 31% by weight of styrene-butadiene block copolymer pellets were prepared.

Subsequently, an asphalt composition was prepared in the same manner as in Example 1.

Comparative example 1: asphalt Modifier And asphalt composition preparation

The weight average molecular weight was about 110 kg/mol in the same manner as in Example 1, except that 0.82 g of dichlorodimethylsilane was used instead of using 4-morpholinecarbonyl chloride, the coupling agent of Example 1, , A styrene block content of 31% by weight of styrene-butadiene block copolymer pellets were prepared.

Subsequently, an asphalt composition was prepared in the same manner as in Example 1.

Experimental example 1: Evaluation of physical properties of the modified asphalt composition

The physical properties of the modified asphalt composition including the asphalt modifier prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

(1) softening point

The softening point is a measure of the high-temperature properties of the modified asphalt measured according to ASTM (American Society Testing and Materials) D36. When heated at 5 ℃ per minute with water or glycerin, the specimen begins to soften and is located on the specimen with a diameter of 9.525 mm and a weight of 3.5. The temperature was measured when g of beads were sagging by 1 inch.

(2) Phase separation Temperature

50 g of the modified asphalt composition was improved in an aluminum tube, left in an oven at 180° C. for 72 hours, and then divided into three parts, and the softening points of the upper part and the lower part were measured by ASTM D36 method, and the temperature difference was calculated.

(3) viscosity

Viscosity 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.

Stirring time
(hr) Example 1 Example 2 Example 3 Comparative Example 1 Softening point
(℃) 3 83.4 83.8 84.0 86 4 76.6 76.8 77.2 85.8 5 65.0 65.2 65.6 82.1 Phase separation temperature
(T, ℃) 3 16.4 15.8 18.0 33.1 4 7.3 6.5 8.0 21.4 5 1.5 0.2 1.8 4.0 Viscosity
(cps) 135 ℃ 5 1625 1630 1635 1675 160 ℃ 590 595 600 625 180 ℃ 300 305 305 315

As shown in Table 1, compared to the modified asphalt composition of Comparative Example 1, in the case of the modified asphalt composition containing the asphalt modifier according to the present invention, the phase separation temperature was large without deteriorating the basic physical properties of the modified asphalt such as softening point, viscosity, and elastic recovery rate. It was confirmed that the solubility in the asphalt composition was greatly improved due to the lowering.

The modified asphalt composition of Example 1 comprising a styrene butadiene block copolymer having a specific multifunctional functional group according to the present invention reduced the phase separation temperature by 50% or more compared to Comparative Example 1 under the same stirring time, through which the modified asphalt composition It was confirmed that the storage stability of was excellent.

The asphalt modifier of the present invention has high compatibility with the asphalt composition and can provide an asphalt composition in which storage stability is effectively modified while maintaining excellent high-temperature properties.

Claims (9)

In the asphalt composition comprising asphalt, a crosslinking agent and an asphalt modifier,
The asphalt modifier is represented by the following formula (1), and includes a vinyl aromatic hydrocarbon-conjugated diene block copolymer main chain and a multifunctional functional group X bonded thereto,
The multifunctional functional group X is derived from a coupling agent containing 4-methyl-1-piperazinecarbonyl chloride,
The asphalt composition is an asphalt composition having a phase separation temperature of 0.2 °C or more and less than 1.5 °C when stirred for 5 hours:
[Formula 1]

(In Formula 1,
A to C blocks are each independently a vinyl aromatic hydrocarbon block or a conjugated diene block, X is a polyfunctional functional group, m, n and o are integers of 0 or more, m+n+o is 2 or more, and p is 0< It is an integer of p≤3.). delete The method of claim 1,
The vinyl aromatic hydrocarbon block is at least one selected from the group consisting of styrene, alpha-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-(para-methylphenyl)styrene. Asphalt composition comprising a. The method of claim 1,
The conjugated diene block is an asphalt composition comprising at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-phenyl-1,3-butadiene . The method of claim 1,
Wherein X is an asphalt composition, characterized in that 40 to 4,700 ppm based on the total weight of the total block copolymer 1. The method of claim 1,
Asphalt composition, characterized in that the weight average molecular weight of the asphalt modifier is 15,000 to 500,000 g/mol. The method of claim 1,
The asphalt modifier comprises the steps of preparing a vinyl aromatic hydrocarbon block through a polymerization reaction of a vinyl aromatic hydrocarbon-based monomer in a hydrocarbon-based solvent using a polymerization initiator;
Mixing the vinyl aromatic hydrocarbon block, a polymerization initiator, and a conjugated diene monomer and performing a polymerization reaction to prepare a vinyl aromatic hydrocarbon-conjugated diene block copolymer; And
Asphalt composition, characterized in that produced by a manufacturing method comprising; mixing the vinyl aromatic hydrocarbon-conjugated diene block copolymer and a coupling agent to couple a multifunctional functional group. The method of claim 7,
Asphalt composition, characterized in that the coupling agent comprises 4-methyl-1-piperazinecarbonyl chloride. delete