Additive composition for modified asphalt and modified asphalt composition comprising same

Abstract

An embodiment of the present specification provides an additive composition for modified asphalt, comprising a copolymer represented by chemical formula 1: <chemical formula 1> (A-C-B)n-X , where A is a block composed of an aromatic vinyl monomer, B is a block composed of a conjugated diene monomer, C is a first coupling agent, X is a second coupling agent, n is an integer of 2 to 4, and the second coupling agent is a non-aromatic compound having two or more epoxy groups.

Description

Additive composition for modified asphalt and modified asphalt composition comprising the same

[0001] The present specification relates to an additive composition for modified asphalt and a modified asphalt composition comprising the same.

[0002] Asphalt, used in the manufacture of road paving and waterproofing sheets, is significantly affected by temperature due to its inherent properties. High temperatures can easily soften and deform it, while low temperatures can easily crack and cause damage. These problems frequently occur when asphalt is paved. Prolonged exposure to high and low temperatures over time, as well as the constant impact from heavy objects like passing vehicles, further exacerbate cracking and destruction of asphalt pavement.

[0003] As a countermeasure to these problems, a method of adding asphalt modifiers to asphalt is known, and polymers such as polybutadiene, ethylene propylene rubber (EPDM, EPR), and styrene block copolymers (SBS, SIS) are used as asphalt modifiers. When asphalt modifiers are mixed into asphalt and used, cracking and destruction of asphalt pavement can be suppressed by improving the resistance of asphalt at high and low temperatures. Due to this effect, the use of modified asphalt with modifiers added to road pavement is increasing in industrial sites.

[0004] Meanwhile, styrene block copolymers used as asphalt modifiers can exhibit improved effects as dosage increases. However, they also have the problem of rapidly increasing asphalt viscosity, making processing difficult. Therefore, there is a need to develop an additive for modified asphalt that can improve asphalt resistance at both high and low temperatures, exhibit low viscosity when mixed with asphalt, enable high-volume use, and enhance the processability of asphalt compositions.

[0005] The present specification is intended to solve the problems of the prior art described above, and one object of the present specification is to provide an additive composition for modified asphalt, which improves the resistance of asphalt at high and low temperatures, exhibits low viscosity when mixed with asphalt, allows for a large amount to be added, and improves the processability of an asphalt composition, and a method for producing the same.

[0006] Another object of the present disclosure is to provide a modified asphalt composition having a softening point equal to or higher than that of conventional modified asphalt compositions.

[0007] Another object of the present specification is to provide a modified asphalt composition having excellent high-temperature and low-temperature properties and storage stability, and having low viscosity and thus excellent processability.

[0008] According to one embodiment of one aspect of the present specification, there is provided an additive composition for modified asphalt, comprising a copolymer represented by the following chemical formula 1:

[0009] <Chemical Formula 1>

[0010] (ACB) n -X

[0011] In the above chemical formula 1, A is a block composed of an aromatic vinyl monomer, B is a block composed of a conjugated diene monomer, C is a first coupling agent, X is a second coupling agent, n is an integer from 2 to 4, and the second coupling agent is a non-aromatic compound having two or more epoxy groups.

[0012] In one embodiment, the first coupling agent may be a compound having two or more vinyl groups.

[0013] In one embodiment, the first coupling agent may be one selected from the group consisting of divinylnaphthalene, divinylbenzene, 2,5-divinylthiophene, trivinylbenzene, 1,4-divinyloxybenzene, methoxy-substituted divinylbenzene, diisopropenylbenzene, 4-(4-(2-isopropenylphenoxy)butyl)styrene, and combinations of two or more thereof.

[0014] In one embodiment, the second coupling agent may be a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups.

[0015] According to another embodiment of one aspect of the present specification, there is provided an additive composition for modified asphalt, comprising a copolymer represented by the following chemical formula 2:

[0016] <Chemical Formula 2>

[0017] (DE) n -Y

[0018] In the above chemical formula 2, D is a block composed of a conjugated diene monomer and an aromatic vinyl monomer, E is a block composed of a conjugated diene monomer, Y is a third coupling agent, and n is an integer from 2 to 4.

[0019] In one embodiment, the block composed of the conjugated diene monomer and the aromatic vinyl monomer may have a diblock, random or tapered structure.

[0020] In one embodiment, the content of the conjugated diene monomer included in the block composed of the conjugated diene monomer and the aromatic vinyl monomer may be 1 to 10 wt% based on the total weight of the conjugated diene monomer included in the copolymer.

[0021] In one embodiment, the third coupling agent may be one selected from the group consisting of dialkyl carbonates, dialkyl malonates, dialkyl phthalates, dialkyl succinates, dialkyl glutarates, dialkyl adipates, dialkyl pimelates, dialkyl suberates, dialkyl sebacates, dialkyl azelates, dialkyl brassylates, dialkyl tetracanedioates, dicarboxylates, tricarboxylates, diester compounds, triester compounds, tetrachlorosilanes, dichlorodimethylsilanes, divinylnaphthalenes, divinylbenzenes, 2,5-divinylthiophenes, trivinylbenzenes, 1,4-divinyloxybenzenes, methoxy-substituted divinylbenzenes, diisopropenylbenzenes, 4-(4-(2-isopropenylphenoxy)butyl)styrenes, and combinations of two or more thereof.

[0022] In one embodiment, the third coupling agent may be a non-aromatic compound having two or more epoxy groups.

[0023] According to another embodiment of one aspect of the present specification, there is provided an additive composition for modified asphalt, comprising a copolymer represented by the following chemical formula 3:

[0024] <Chemical Formula 3>

[0025] (FG) n -Z

[0026] In the above chemical formula 3, F is a block including an aromatic vinyl monomer, G is a block including a conjugated diene monomer, Z is a fourth coupling agent, n is an integer from 2 to 4, and the fourth coupling agent is a non-aromatic compound having two or more epoxy groups.

[0027] In one embodiment, the block comprising the aromatic vinyl monomer may be a block composed of an aromatic vinyl monomer; or a block composed of an aromatic vinyl monomer and a conjugated diene monomer.

[0028] In one embodiment, the block composed of the aromatic vinyl monomer and the conjugated diene monomer may have a diblock, random or tapered structure.

[0029] In one embodiment, the fourth coupling agent may be a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups.

[0030] In one embodiment, the content of aromatic vinyl monomer in the copolymer may be 10 to 60 wt%.

[0031] In one embodiment, the vinyl content of the block composed of the conjugated diene monomer may be 10 to 80 mol%.

[0032] In one embodiment, the weight average molecular weight (Mw) of the copolymer may be 20,000 to 1,000,000 g / mol.

[0033] According to another aspect of the present disclosure, a modified asphalt composition is provided, comprising the additive composition for the modified asphalt.

[0034] In one embodiment, the content of the additive composition for modified asphalt may be 0.5 to 40 parts by weight based on 100 parts by weight of the asphalt.

[0035] An additive composition for modified asphalt according to one aspect of the present specification can improve the resistance of asphalt at high and low temperatures, and at the same time exhibit low viscosity when mixed with asphalt, so that a large amount can be added, and can improve the processability of the modified asphalt composition.

[0036] Additionally, the modified asphalt composition according to another aspect of the present disclosure may exhibit a softening point that is equal to or higher than that of a conventional modified asphalt composition.

[0037] In addition, the modified asphalt composition according to another aspect of the present specification can exhibit excellent high-temperature and low-temperature properties and storage stability, while also exhibiting excellent processability due to low viscosity.

[0038] The effects of this specification are not limited to the effects described above, but should be understood to include all effects that can be inferred from the detailed description or claims of this specification.

[0039] Below, aspects of this specification will be described based on specific examples. However, the contents of this specification may be implemented in various different forms and are therefore not limited to the embodiments described herein.

[0040] Throughout the specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise stated.

[0041] When a range of numerical values ​​is stated herein, unless the specific range is otherwise specified, the values ​​have the precision of the significant figures provided according to the standard rules in chemistry for significant figures. For example, the number 10 includes the range of 5.0 to 14.9, and the number 10.0 includes the range of 9.50 to 10.49.

[0042] Additive composition for modified asphalt

[0043] The present invention has been completed based on the finding that when a copolymer included in an additive composition for modified asphalt includes a specific block or is coupled by a specific coupling agent, the processability of the asphalt composition can be improved. The additive composition for modified asphalt, which is one aspect of the present specification, can be broadly divided into three embodiments according to the chemical structure of the copolymer. Each embodiment will be described in detail below.

[0044] First embodiment

[0045] An additive composition for modified asphalt according to the first embodiment comprises a copolymer represented by the following chemical formula 1.

[0046] <Chemical Formula 1>

[0047] (ACB) n -X

[0048] In the above chemical formula 1, A is a block composed of an aromatic vinyl monomer, B is a block composed of a conjugated diene monomer, C is a first coupling agent, X is a second coupling agent, n is an integer from 2 to 4, and the second coupling agent is a non-aromatic compound having two or more epoxy groups.

[0049] The above aromatic vinyl monomers are styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 5-tert-butyl-2-methylstyrene, tert-butoxystyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, N,N-dimethylaminoethylstyrene, 1-vinyl-5-hexylnaphthalene, 1-vinylnaphthalene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, vinylpyridine, vinylxylene, diphenylethylene, diphenylethylene containing a tertiary amine, primary, secondary, or tertiary It may be one selected from the group consisting of styrene containing amine and combinations of two or more thereof, but is not limited thereto.

[0050] The above conjugated diene monomer may be one selected from the group consisting of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chloro-1,3-butadiene, 3-butyl-1,3-octadiene, octadiene, and combinations of two or more thereof, but is not limited thereto.

[0051] The first coupling agent and the second coupling agent may be of the same or different types. The above-mentioned additive composition for modified asphalt may be manufactured by reacting two or more coupling agents simultaneously or sequentially, and thus may have a higher coupling number than a copolymer manufactured using one type of coupling agent, or even if the coupling number is the same, may have higher solubility in asphalt and thus exhibit lower solution viscosity, and thus exhibit excellent processability, workability, and storage stability.

[0052] The first coupling agent may be a compound having two or more vinyl groups. When the first coupling agent is a compound having two or more vinyl groups and the second coupling agent is a non-aromatic compound having two or more epoxy groups, the number of couplings increases compared to a conventional modified asphalt additive composition, so that the viscosity of the modified asphalt composition can be reduced, and even when the number of couplings is the same, the high-temperature characteristics such as the softening point, the low-temperature characteristics such as the foam breaking point, and the storage stability of the modified asphalt composition can be balanced and improved.

[0053] The first coupling agent is divinylnaphthalene (e.g., 1,4-divinylnaphthalene, 1,6-divinylnaphthalene, 1,8-divinylnaphthalene, 2,7-divinylnaphthalene), divinylbenzene (e.g., 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene), 2,5-divinylthiophene (e.g., 3-hexyl-2,5-divinylthiophene, 3-methyl-2,5-divinylthiophene), trivinylbenzene (e.g., 1,2,3-trivinylbenzene, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene), 1,4-divinyloxybenzene, methoxy-substituted divinylbenzene (e.g., 2-methoxy-1,4-divinylbenzene, 4-methoxy-1,2-divinylbenzene, 4-methoxy-1,3-divinylbenzene, 2-methoxy-1,3-divinylbenzene, 5-methoxy-1,3-divinylbenzene), diisopropenylbenzene (e.g., 1,4-diisopropenylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene), 4-(4-(2-isopropenylphenoxy)butyl)styrene, and a combination of two or more thereof, for example, but not limited to, divinylbenzene.

[0054] The second coupling agent includes a non-aromatic compound having two or more epoxy groups, and accordingly, the modified asphalt additive composition manufactured by the method has a higher coupling number than a conventional modified asphalt additive composition, or even if the coupling number is the same, has high solubility in asphalt and exhibits low solution viscosity, and thus can exhibit excellent processability, workability, and storage stability.

[0055] The second coupling agent may include a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups. When the second coupling agent includes a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups, the modified asphalt additive composition produced by the method may exhibit a higher coupling number compared to a conventional modified asphalt additive composition, and accordingly, exhibit a lower viscosity when mixed with asphalt, so that a larger amount of the additive composition can be added to the asphalt compared to a conventional one.

[0056] The second coupling agent may be a mixture of a non-aromatic compound having two or more epoxy groups and no halogenated alkyl group, and a non-aromatic compound having both two or more epoxy groups and one or more halogenated alkyl group. For example, the second coupling agent may be a mixture including 40 to 60 wt% of a non-aromatic compound having two or more epoxy groups and no halogenated alkyl group, and 40 to 60 wt% of a non-aromatic compound having both two or more epoxy groups and one or more halogenated alkyl group, but is not limited thereto.

[0057] The second coupling agent may be, but is not limited to, a mixture of a non-aromatic compound having two epoxy groups and no halogenated alkyl group, a non-aromatic compound having two epoxy groups and one halogenated alkyl group, and a non-aromatic compound having two epoxy groups and two halogenated alkyl groups.

[0058] The above halogenated alkyl group may be one selected from the group consisting of an alkyl chloride, an alkyl fluoride, an alkyl bromide, an alkyl iodide, and a combination of two or more thereof.

[0059] The second coupling agent may be a hydrogenated bisphenol A type epoxy resin. The hydrogenated bisphenol A type epoxy resin has less yellowing than a bisphenol A type epoxy resin containing an aromatic compound, thus exhibiting excellent weather resistance, has low viscosity, and exhibits excellent handling properties, thereby reducing the viscosity of the modified asphalt composition.

[0060] The second coupling agent may be, but is not limited to, a reaction product of hydrogenated bisphenol A and epichlorohydrin (CAS No. 30583-72-3).

[0061] The content of the aromatic vinyl monomer in the above copolymer may be 10 to 60 wt%, preferably 15 to 40 wt%, but is not limited thereto. For example, it may be 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or a range between any two of these values. If the content of the aromatic vinyl monomer is less than the above range, the softening point of the modified asphalt composition may be lowered, and if it exceeds the above range, the low-temperature properties may be lowered.

[0062] The vinyl content of the block composed of the above conjugated diene monomer may be 10 to 80 mol%, preferably 50 to 70 mol%, but is not limited thereto. For example, it may be 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, or a range between any two of these values. When the vinyl content of the block composed of the conjugated diene monomer satisfies the above range, it can exhibit excellent solubility in asphalt. When the vinyl content is less than the above range, the high-temperature properties of the modified asphalt composition may deteriorate, and when it exceeds the above range, the storage stability may deteriorate or the viscosity may increase.

[0063] The weight average molecular weight (Mw) of the above copolymer may be 20,000 to 1,000,000 g / mol, preferably 20,000 to 300,000 g / mol, and more preferably 20,000 to 150,000 g / mol, but is not limited thereto. For example, 20,000 g / mol, 40,000 g / mol, 60,000 g / mol, 80,000 g / mol, 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol, 140,000 g / mol, 150,000 g / mol, 160,000 g / mol, 170,000 g / mol, 180,000 g / mol, 190,000 g / mol, 200,000 g / mol, 300,000 g / mol, 400,000 g / mol, 500,000 g / mol, 600,000 g / mol, 700,000 g / mol, It may be 800,000 g / mol, 900,000 g / mol, 1,000,000 g / mol, or a range between any two of these values. If the weight average molecular weight of the copolymer is less than the above range, the high-temperature properties such as the softening point of the modified asphalt composition may be reduced, or the mechanical application properties may not be easily expressed, and if it is more than the above range, the storage stability may be reduced, or the viscosity may increase, resulting in reduced processability.

[0064] In addition to the copolymer represented by the above chemical formula 1, the above-mentioned additive composition for modified asphalt may further include, but is not limited to, a block copolymer in which a block composed of an aromatic vinyl monomer and a block composed of a conjugated diene monomer are directly bonded without a coupling agent, a copolymer in which the block copolymers are bonded to each other or bonded through a coupling agent, etc.

[0065] In the present specification, a method for producing the above-described additive composition for modified asphalt is not particularly limited, but, for example, the additive composition for modified asphalt may be produced by including the steps of: (a) polymerizing an aromatic vinyl monomer in the presence of an initiator; (b) adding a first coupling agent to the product of step (a) and causing it to react; (c) adding a conjugated diene monomer to the product of step (b) and causing it to polymerize; and (d) adding a second coupling agent to the product of step (c) and causing it to react.

[0066] The types of monomer, first coupling agent and second coupling agent used in the above manufacturing method are the same as those described above.

[0067] The above step (a) is a step of polymerizing an aromatic vinyl monomer in the presence of an initiator to form a block composed of the aromatic vinyl monomer. In the above step (a), the polymerization reaction of the aromatic vinyl monomer is initiated, so that a living polymer can be produced.

[0068] The above initiator may be an organic lithium compound such as n-butyllithium, but is not limited thereto, and a conventional anionic initiator may be used.

[0069] The above step (a) may include a step of introducing an aromatic vinyl monomer and an initiator into a reactor.

[0070] The above step (a) may further include a step of introducing a polar modifier into the reactor. When the polar modifier is introduced, the vinyl content of the block composed of the conjugated diene monomer can be controlled.

[0071] The above polar modifier may be one selected from the group consisting of ditetrahydrofurylpropane (DTHFP), tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), and a combination of two or more thereof, but is not limited thereto.

[0072] In the step (b), some of the living polymer can be coupled with the residue of the first coupling agent.

[0073] The above step (c) is a step of polymerizing a conjugated diene monomer to form a block composed of the conjugated diene monomer. In the above step (c), the living polymer coupled with the first coupling agent can react with a polymer of the conjugated diene monomer to form a block copolymer represented by the following chemical formula 1P.

[0074] <Chemical Formula 1P>

[0075] ACB

[0076] In the above chemical formula 1P, A is a block composed of an aromatic vinyl monomer, B is a block composed of a conjugated diene monomer, and C is a first coupling agent.

[0077] The weight average molecular weight (Mw) of the block copolymer represented by the above chemical formula 1P may be 5,000 to 500,000 g / mol. For example, 5,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, 95,000 g / mol, 100,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, or a range between any two of these values. If the weight average molecular weight of the block copolymer represented by the above chemical formula 1P is less than the above range, the high-temperature properties of the modified asphalt composition may deteriorate, and if it exceeds the above range, the viscosity may increase, resulting in deterioration in processability or deterioration in storage stability.

[0078] In the above step (d), a portion of the block copolymer represented by the chemical formula 1P may be coupled with a residue of the second coupling agent.

[0079] The total weight average molecular weight (Mw) of the additive composition for modified asphalt manufactured by the above method may be 5,000 to 500,000 g / mol. For example, 5,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, 95,000 g / mol, 100,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, or a range between any two of these values. If the total weight average molecular weight is less than the above range, the high temperature properties of the modified asphalt composition may be deteriorated, and if it is more than the above range, the viscosity may increase, which may result in deterioration of processability, deterioration of storage stability, or a decrease in the amount of additives that can be added to the asphalt.

[0080] The coupling efficiency of the additive composition for modified asphalt manufactured by the above method may be 15 to 96%, preferably 15 to 40%, but is not limited thereto. For example, it may be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, or a range between any two of these values. If the coupling efficiency is below the above range, the high-temperature characteristics, such as the softening point, of the modified asphalt composition may deteriorate, and if it exceeds the above range, the storage stability may deteriorate or the viscosity may increase, resulting in reduced processability.

[0081] Second embodiment

[0082] An additive composition for modified asphalt according to the second embodiment comprises a copolymer represented by the following chemical formula 2.

[0083] <Chemical Formula 2>

[0084] (DE) n -Y

[0085] In the above chemical formula 2, D is a block composed of a conjugated diene monomer and an aromatic vinyl monomer, E is a block composed of a conjugated diene monomer, Y is a third coupling agent, and n is an integer from 2 to 4.

[0086] The second embodiment is a case where the chemical structure of the copolymer is different compared to the first embodiment, and the description overlapping with the first embodiment will be omitted.

[0087] The above-described additive composition for modified asphalt includes a copolymer including a block composed of a conjugated diene monomer and an aromatic vinyl monomer, thereby exhibiting lower viscosity when mixed with asphalt compared to a conventional additive composition for modified asphalt, enabling a large amount to be added to asphalt, and improving the processability of the asphalt composition, thereby exhibiting improved stability.

[0088] The block composed of the above conjugated diene monomer and aromatic vinyl monomer may have a diblock, random or tapered structure, but is not limited thereto.

[0089] The above diblock structure refers to a structure in which a block composed of a conjugated diene monomer and a block composed of an aromatic vinyl monomer are combined. When the block composed of the conjugated diene monomer and the aromatic vinyl monomer is a diblock structure, the above chemical formula 2 is (block composed of a conjugated diene monomer - block composed of an aromatic vinyl monomer - E) n -It can be a structure of Y, but is not limited to this.

[0090] The above random structure means a structure in which conjugated diene monomers and aromatic vinyl monomers are randomly distributed within the block.

[0091] The above tapered structure refers to a structure in which the ratio of a specific monomer is distributed in a form that gradually changes from one end of the block to the other end.

[0092] Based on the total weight of the conjugated diene monomer included in the copolymer, the content of the conjugated diene monomer included in the block composed of the conjugated diene monomer and the aromatic vinyl monomer may be 1 to 10 wt%. For example, it may be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, or a range between any two values ​​therebetween. If the content of the conjugated diene monomer included in the block composed of the conjugated diene monomer and the aromatic vinyl monomer exceeds the above range, the high-temperature and low-temperature properties of the modified asphalt composition may deteriorate.

[0093] The third coupling agent is dialkyl carbonate, dialkyl malonate, dialkyl phthalate, dialkyl succinate, dialkyl glutarate, dialkyl adipate, dialkyl pimelate, dialkyl suberate, dialkyl sebacate, dialkyl azelate, dialkyl brassylate, dialkyl tetracanedioate, dicarboxylate, tricarboxylate, diester compound, triester compound, tetrachlorosilane, dichlorodimethylsilane, divinyl naphthalene (e.g., 1,4-divinyl naphthalene, 1,6-divinyl naphthalene, 1,8-divinyl naphthalene, 2,7-divinyl naphthalene), divinyl benzene (e.g., 1,2-divinyl benzene, 1,3-divinyl benzene, 1,4-divinyl benzene), 2,5-divinyl thiophene (e.g., 3-hexyl-2,5-divinylthiophene, 3-methyl-2,5-divinylthiophene), trivinylbenzenes (e.g., 1,2,3-trivinylbenzene, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene), 1,4-divinyloxybenzene, methoxy-substituted divinylbenzenes (e.g., 2-methoxy-1,4-divinylbenzene, 4-methoxy-1,2-divinylbenzene, 4-methoxy-1,3-divinylbenzene, 2-methoxy-1,3-divinylbenzene, 5-methoxy-1,3-divinylbenzene), diisopropenylbenzenes (e.g., 1,4-diisopropenylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene), It may be one selected from the group consisting of 4-(4-(2-isopropenylphenoxy)butyl)styrene and combinations of two or more thereof, but is not limited thereto, and may be a typical 2- to 4-valent coupling agent.

[0094] The third coupling agent includes a non-aromatic compound having two or more epoxy groups, and accordingly, the modified asphalt additive composition manufactured by the method has a higher coupling number than a conventional modified asphalt additive composition, or even if the coupling number is the same, has high solubility in asphalt and exhibits low solution viscosity, and thus can exhibit excellent processability, workability, and storage stability.

[0095] The third coupling agent may include a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups. When the third coupling agent includes a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups, the modified asphalt additive composition produced by the method may exhibit a higher coupling number compared to a conventional modified asphalt additive composition, and accordingly, exhibit a lower viscosity when mixed with asphalt, so that a larger amount of the additive composition can be added to the asphalt compared to a conventional one.

[0096] The third coupling agent may be a mixture of a non-aromatic compound having two or more epoxy groups and no halogenated alkyl group, and a non-aromatic compound having both two or more epoxy groups and one or more halogenated alkyl groups. For example, the third coupling agent may be a mixture including, but not limited to, 40 to 60 wt% of a non-aromatic compound having two or more epoxy groups and no halogenated alkyl group, and 40 to 60 wt% of a non-aromatic compound having both two or more epoxy groups and one or more halogenated alkyl groups.

[0097] The third coupling agent may be, but is not limited to, a mixture of a non-aromatic compound having two epoxy groups and no halogenated alkyl group, a non-aromatic compound having two epoxy groups and one halogenated alkyl group, and a non-aromatic compound having two epoxy groups and two halogenated alkyl groups.

[0098] The above halogenated alkyl group may be one selected from the group consisting of an alkyl chloride, an alkyl fluoride, an alkyl bromide, an alkyl iodide, and a combination of two or more thereof.

[0099] The third coupling agent may be a hydrogenated bisphenol A type epoxy resin. The hydrogenated bisphenol A type epoxy resin has less yellowing than a bisphenol A type epoxy resin containing an aromatic compound, thus exhibiting excellent weather resistance, has low viscosity, and exhibits excellent handling properties, thereby reducing the viscosity of the modified asphalt composition.

[0100] The third coupling agent may be, but is not limited to, a reaction product of hydrogenated bisphenol A and epichlorohydrin (CAS No. 30583-72-3).

[0101] In the present specification, the method for producing the additive composition for modified asphalt is not particularly limited, but may be produced by, for example, including: (a) a step of simultaneously or sequentially polymerizing a conjugated diene monomer and an aromatic vinyl monomer in the presence of an initiator; (b) a step of introducing a conjugated diene monomer into the product of step (a) and polymerizing it; and (c) a step of introducing a third coupling agent into the product of step (b) and reacting it.

[0102] The types of monomers and third coupling agents used in the above manufacturing method are the same as those described above.

[0103] The above step (a) is a step of polymerizing a conjugated diene monomer and an aromatic vinyl monomer simultaneously or sequentially in the presence of an initiator to form a block composed of the conjugated diene monomer and the aromatic vinyl monomer. In the above step (a), the polymerization reaction of the conjugated diene monomer and the aromatic vinyl monomer is initiated, so that a living polymer can be produced.

[0104] The above step (a) may include a step of simultaneously or sequentially introducing a conjugated diene monomer and an aromatic vinyl monomer into the reactor.

[0105] Based on the total weight of the conjugated diene monomer polymerized in steps (a) and (b), the weight ratio of the conjugated diene monomer polymerized in step (a) may be 1 to 10 wt%. For example, it may be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, or a range between any two of these values. If the weight ratio of the conjugated diene monomer polymerized in step (a) exceeds the above range, the high-temperature and low-temperature properties of the modified asphalt composition may deteriorate.

[0106] The above step (b) is a step of polymerizing a conjugated diene monomer to form a block composed of the conjugated diene monomer. In the above step (b), the living polymer can react with a polymer of the conjugated diene monomer to form a block copolymer represented by the following chemical formula 2P.

[0107] <Chemical Formula 2P>

[0108] DE

[0109] In the above chemical formula 2P, D is a block composed of a conjugated diene monomer and an aromatic vinyl monomer, and E is a block composed of a conjugated diene monomer.

[0110] In the step (a) above, when the conjugated diene monomer and the aromatic vinyl monomer are polymerized simultaneously, D in the chemical formula 2P may have a random or tapered structure. The random structure refers to a structure in which the conjugated diene monomer and the aromatic vinyl monomer are randomly distributed within the block. The tapered structure refers to a structure in which the ratio of a specific monomer is distributed in a form in which it gradually changes from one end of the block to the other end.

[0111] In the step (a) above, when a conjugated diene monomer and an aromatic vinyl monomer are sequentially polymerized, D of the chemical formula 2P may be a diblock structure in which a block composed of a conjugated diene monomer and a block composed of an aromatic vinyl monomer are combined.

[0112] The weight average molecular weight (Mw) of the block copolymer represented by the above chemical formula 2P may be 5,000 to 500,000 g / mol. For example, 5,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, 95,000 g / mol, 100,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, or a range between any two of these values. If the weight average molecular weight of the block copolymer represented by the above chemical formula 2P is less than the above range, the high-temperature properties of the modified asphalt composition may deteriorate, and if it exceeds the above range, the viscosity may increase, resulting in deterioration in processability or deterioration in storage stability.

[0113] In the above step (c), a portion of the block copolymer represented by the chemical formula 2P may be coupled with a residue of the third coupling agent.

[0114] The total weight average molecular weight (Mw) of the additive composition for modified asphalt manufactured by the above method may be 5,000 to 500,000 g / mol. For example, 5,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, 95,000 g / mol, 100,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, or a range between any two of these values. If the total weight average molecular weight is less than the above range, the high temperature properties of the modified asphalt composition may be deteriorated, and if it is more than the above range, the viscosity may increase, which may result in deterioration of processability, deterioration of storage stability, or a decrease in the amount of additives that can be added to the asphalt.

[0115] The coupling efficiency of the additive composition for modified asphalt manufactured by the above method may be 15 to 96%, preferably 15 to 40%, but is not limited thereto. For example, it may be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, or a range between any two of these values. If the coupling efficiency is below the above range, the high-temperature characteristics, such as the softening point, of the modified asphalt composition may deteriorate, and if it exceeds the above range, the storage stability may deteriorate or the viscosity may increase, resulting in reduced processability.

[0116] Third embodiment

[0117] An additive composition for modified asphalt according to the third embodiment comprises a copolymer represented by the following chemical formula 3.

[0118] <Chemical Formula 3>

[0119] (FG) n -Z

[0120] In the above chemical formula 3, F is a block including an aromatic vinyl monomer, G is a block including a conjugated diene monomer, Z is a fourth coupling agent, n is an integer from 2 to 4, and the fourth coupling agent is a non-aromatic compound having two or more epoxy groups.

[0121] The third embodiment is a case where the chemical structure of the copolymer is different compared to the first embodiment, and the description overlapping with the first embodiment will be omitted.

[0122] The block comprising the above aromatic vinyl monomer may be, but is not limited to, a block composed of an aromatic vinyl monomer; or a block composed of an aromatic vinyl monomer and a conjugated diene monomer.

[0123] Based on the total weight of the conjugated diene monomer included in the copolymer, the content of the conjugated diene monomer included in the block composed of the aromatic vinyl monomer and the conjugated diene monomer may be 1 to 10 wt%. For example, it may be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, or a range between any two of these values. If the content of the conjugated diene monomer included in the block composed of the aromatic vinyl monomer and the conjugated diene monomer exceeds the above range, the high-temperature and low-temperature properties of the modified asphalt composition may deteriorate.

[0124] The block composed of the above aromatic vinyl monomer and conjugated diene monomer may have a diblock, random or tapered structure, but is not limited thereto.

[0125] The above diblock structure refers to a structure in which a block composed of a conjugated diene monomer and a block composed of an aromatic vinyl monomer are combined. When the block composed of the aromatic vinyl monomer and the conjugated diene monomer is a diblock structure, the above chemical formula 3 is (block composed of a conjugated diene monomer - block composed of an aromatic vinyl monomer - G) n -It can be a structure of Z, but is not limited to this.

[0126] The above random structure means a structure in which conjugated diene monomers and aromatic vinyl monomers are randomly distributed within the block.

[0127] The above tapered structure refers to a structure in which the ratio of a specific monomer is distributed in a form that gradually changes from one end of the block to the other end.

[0128] The above-described modified asphalt additive composition uses a non-aromatic compound having two or more epoxy groups as a fourth coupling agent, thereby having a higher coupling number than a conventional modified asphalt additive composition, or even if the coupling number is the same, having higher solubility in asphalt and thus exhibiting low solution viscosity, and thus exhibiting excellent processability, workability, and storage stability.

[0129] The fourth coupling agent may include a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups. When the fourth coupling agent includes a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups, the modified asphalt additive composition produced by the method may exhibit a higher coupling number compared to a conventional modified asphalt additive composition, and accordingly, exhibit a lower viscosity when mixed with asphalt, so that a larger amount of the additive composition can be added to the asphalt compared to a conventional one.

[0130] The fourth coupling agent may be a mixture of a non-aromatic compound having two or more epoxy groups and no halogenated alkyl group, and a non-aromatic compound having both two or more epoxy groups and one or more halogenated alkyl groups. For example, the fourth coupling agent may be a mixture including, but not limited to, 40 to 60 wt% of a non-aromatic compound having two or more epoxy groups and no halogenated alkyl group, and 40 to 60 wt% of a non-aromatic compound having both two or more epoxy groups and one or more halogenated alkyl groups.

[0131] The fourth coupling agent may be, but is not limited to, a mixture of a non-aromatic compound having two epoxy groups and no halogenated alkyl group, a non-aromatic compound having two epoxy groups and one halogenated alkyl group, and a non-aromatic compound having two epoxy groups and two halogenated alkyl groups.

[0132] The above halogenated alkyl group may be one selected from the group consisting of an alkyl chloride, an alkyl fluoride, an alkyl bromide, an alkyl iodide, and a combination of two or more thereof.

[0133] The fourth coupling agent may be a hydrogenated bisphenol A type epoxy resin. The hydrogenated bisphenol A type epoxy resin has less yellowing than a bisphenol A type epoxy resin containing an aromatic compound, thus exhibiting excellent weather resistance, has low viscosity, and exhibits excellent handling properties, thereby reducing the viscosity of the modified asphalt composition.

[0134] The fourth coupling agent may be, but is not limited to, a reaction product of hydrogenated bisphenol A and epichlorohydrin (CAS No. 30583-72-3).

[0135] The content of the aromatic vinyl monomer in the above copolymer may be 10 to 60 wt%, preferably 15 to 40 wt%, but is not limited thereto. For example, it may be 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or a range between any two of these values. If the content of the aromatic vinyl monomer is less than the above range, the softening point of the modified asphalt composition may be lowered, and if it exceeds the above range, the low-temperature properties may be lowered.

[0136] The vinyl content of the block composed of the above conjugated diene monomer may be 10 to 80 mol%, preferably 50 to 70 mol%, but is not limited thereto. For example, it may be 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, or a range between any two of these values. When the vinyl content of the block composed of the conjugated diene monomer satisfies the above range, it can exhibit excellent solubility in asphalt. When the vinyl content is less than the above range, the high-temperature properties of the modified asphalt composition may deteriorate, and when it exceeds the above range, the storage stability may deteriorate or the viscosity may increase.

[0137] The weight average molecular weight (Mw) of the above copolymer may be 20,000 to 1,000,000 g / mol, preferably 20,000 to 300,000 g / mol, and more preferably 20,000 to 150,000 g / mol, but is not limited thereto. For example, 20,000 g / mol, 40,000 g / mol, 60,000 g / mol, 80,000 g / mol, 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol, 140,000 g / mol, 150,000 g / mol, 160,000 g / mol, 170,000 g / mol, 180,000 g / mol, 190,000 g / mol, 200,000 g / mol, 300,000 g / mol, 400,000 g / mol, 500,000 g / mol, 600,000 g / mol, 700,000 g / mol, It may be 800,000 g / mol, 900,000 g / mol, 1,000,000 g / mol, or a range between any two of these values. If the weight average molecular weight of the copolymer is less than the above range, the high-temperature properties such as the softening point of the modified asphalt composition may be reduced, or the mechanical application properties may not be easily expressed, and if it is more than the above range, the storage stability may be reduced, or the viscosity may increase, resulting in reduced processability.

[0138] In addition to the copolymer represented by the above chemical formula 3, the above-mentioned additive composition for modified asphalt may further include, but is not limited to, a block copolymer in which only a block including an aromatic vinyl monomer and a block composed of a conjugated diene monomer are combined, a copolymer in which the block copolymer is combined without a coupling agent, etc.

[0139] In the present specification, the method for producing the additive composition for modified asphalt is not particularly limited, but includes, for example, (a) a step of polymerizing an aromatic vinyl monomer in the presence of an initiator; (b) a step of introducing a conjugated diene monomer into the product of step (a) and polymerizing it; and (c) a step of introducing a fourth coupling agent into the product of step (b) and reacting it; wherein the fourth coupling agent can be produced by including a non-aromatic compound having two or more epoxy groups.

[0140] The types of monomers and fourth coupling agent used in the above manufacturing method are the same as those described above.

[0141] The above step (a) is a step of polymerizing an aromatic vinyl monomer in the presence of an initiator to form a block including the aromatic vinyl monomer. In the above step (a), the polymerization reaction of the aromatic vinyl monomer is initiated, so that a living polymer can be produced.

[0142] The above initiator may be an organic lithium compound such as n-butyllithium, but is not limited thereto, and a conventional anionic initiator may be used.

[0143] The above step (a) may include a step of introducing an aromatic vinyl monomer and an initiator into a reactor.

[0144] The above step (a) may further include a step of introducing a polar modifier into the reactor. When the polar modifier is introduced, the vinyl content of the block composed of the conjugated diene monomer can be controlled.

[0145] The above polar modifier may be one selected from the group consisting of ditetrahydrofurylpropane (DTHFP), tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), and a combination of two or more thereof, but is not limited thereto.

[0146] The step (a) above may further include a step of polymerizing a conjugated diene monomer. The conjugated diene monomer of the step (a) may be polymerized by introducing it simultaneously with or sequentially from the aromatic vinyl monomer. The amount of the conjugated diene monomer introduced in the step (a) may be 1 to 10 wt% based on the total weight of the conjugated diene monomer introduced in the manufacturing method.

[0147] The above step (b) is a step of polymerizing a conjugated diene monomer to form a block composed of the conjugated diene monomer. In the above step (b), the living polymer can react with a polymer of the conjugated diene monomer to form a block copolymer represented by the following chemical formula 3P.

[0148] <Chemical Formula 3P>

[0149] FG

[0150] In the above chemical formula 3P, F is a block containing an aromatic vinyl monomer, and G is a block composed of a conjugated diene monomer.

[0151] In the step (a) above, when a conjugated diene monomer and an aromatic vinyl monomer are simultaneously introduced and polymerized, F in the chemical formula 3P may have a random or tapered structure. The random structure refers to a structure in which the conjugated diene monomer and the aromatic vinyl monomer are randomly distributed within the block. The tapered structure refers to a structure in which the ratio of a specific monomer is distributed in a form in which it gradually changes from one end of the block to the other end.

[0152] In the step (a) above, when a conjugated diene monomer and an aromatic vinyl monomer are sequentially introduced and polymerized, A of the chemical formula 3P may be a diblock structure in which a block composed of a conjugated diene monomer and a block composed of an aromatic vinyl monomer are combined.

[0153] The weight average molecular weight (Mw) of the block copolymer represented by the above chemical formula 3P may be 5,000 to 500,000 g / mol. For example, 5,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, 95,000 g / mol, 100,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, or a range between any two of these values. If the weight average molecular weight of the block copolymer represented by the above chemical formula 3P is less than the above range, the high-temperature properties of the modified asphalt composition may deteriorate, and if it exceeds the above range, the viscosity may increase, resulting in deterioration in processability or deterioration in storage stability.

[0154] In the above step (c), a part of the block copolymer represented by the chemical formula 3P can be coupled with a residue of the fourth coupling agent.

[0155] The total weight average molecular weight (Mw) of the additive composition for modified asphalt manufactured by the above method may be 5,000 to 500,000 g / mol. For example, 5,000 g / mol, 10,000 g / mol, 15,000 g / mol, 20,000 g / mol, 25,000 g / mol, 30,000 g / mol, 35,000 g / mol, 40,000 g / mol, 45,000 g / mol, 50,000 g / mol, 55,000 g / mol, 60,000 g / mol, 65,000 g / mol, 70,000 g / mol, 75,000 g / mol, 80,000 g / mol, 85,000 g / mol, 90,000 g / mol, 95,000 g / mol, 100,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, or a range between any two of these values. If the total weight average molecular weight is less than the above range, the high temperature properties of the modified asphalt composition may be deteriorated, and if it is more than the above range, the viscosity may increase, which may result in deterioration of processability, deterioration of storage stability, or a decrease in the amount of additives that can be added to the asphalt.

[0156] The coupling efficiency of the additive composition for modified asphalt manufactured by the above method may be 15 to 96%, preferably 15 to 40%, but is not limited thereto. For example, it may be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, or a range between any two of these values. If the coupling efficiency is below the above range, the high-temperature characteristics, such as the softening point, of the modified asphalt composition may deteriorate, and if it exceeds the above range, the storage stability may deteriorate or the viscosity may increase, resulting in reduced processability.

[0157] Modified asphalt composition

[0158] According to another aspect of the present disclosure, a modified asphalt composition comprises asphalt; and an additive composition for modified asphalt.

[0159] The above-described additive composition for modified asphalt may include a copolymer represented by the above-described chemical formula 1, chemical formula 2, or chemical formula 3. In another example, the above-described additive composition for modified asphalt may be manufactured by the above-described manufacturing method, but is not limited thereto.

[0160] Based on 100 parts by weight of the asphalt, the content of the additive composition for modified asphalt may be 0.5 to 40 parts by weight. For example, it may be 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, or a range between any two of these values. If the content of the additive composition for modified asphalt is below the above range, the concentration of the polymer is too low to exhibit performance as a modifier, and if it exceeds the above range, the viscosity increases, so that the dispersibility between the asphalt and the additive composition for modified asphalt and the flowability of the modified asphalt composition are reduced, and the dispersion time may be delayed.

[0161] The modified asphalt composition described above can have a softening point equal to or higher than that of conventional modified asphalt compositions, while simultaneously exhibiting excellent low-temperature properties and storage stability, and exhibiting excellent processability due to its low viscosity. Due to these excellent properties, the modified asphalt composition can be free of sulfur-based cross-linking agents, thereby exhibiting environmentally friendly properties.

[0162] The above modified asphalt composition can be used for road paving, waterproofing sheets, or sealants, but is not limited thereto.

[0163] Hereinafter, the embodiments of this specification will be described in more detail. However, the experimental results below represent only representative experimental results among the above embodiments, and the scope and content of this specification cannot be interpreted as being reduced or limited by the embodiments, etc. The effects of each of the various implementation examples of this specification that are not explicitly presented below will be specifically described in the relevant sections.

[0164] Example 1-1

[0165] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of polar modifier, and 132 g of styrene were injected into the reactor, and the temperature was maintained at 50°C. 0.21 phm of n-butyllithium as an initiator was injected into the reactor to initiate the polymerization reaction. When the polymerization temperature reached the maximum temperature, 0.0132 phm of divinylbenzene (DVB) was injected, and 268 g of butadiene was added 10 minutes later to proceed with the polymerization. 5 minutes after the polymerization temperature reached the maximum temperature, 0.10 phm of KER-950 (Kumho P&B Chemical Co., Ltd., CAS No. 30583-72-3) as a coupling agent was added to proceed with the coupling. After 15 minutes, caprylic acid, a polymerization terminator, was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the terminated polymerization solution, and cyclohexane was removed using a roll mill to produce a copolymer.

[0166] Example 1-2

[0167] A copolymer was prepared in the same manner as in Example 1-1, except that 0.15 phm of n-butyllithium was added.

[0168] Example 1-3

[0169] A copolymer was prepared in the same manner as in Example 1-1, except that 0.19 phm of n-butyllithium and 0.0264 phm of divinylbenzene were added.

[0170] Example 1-4

[0171] A copolymer was prepared in the same manner as in Example 1-3, except that 0.17 phm of n-butyllithium was added.

[0172] Example 1-5

[0173] A copolymer was prepared in the same manner as in Example 1-3, except that 0.17 phm of n-butyllithium and 0.09 phm of KER-950 were added.

[0174] Comparative Example 1-1

[0175] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of polar modifier, and 132 g of styrene were injected into the reactor, and the temperature was maintained at 50°C. 0.21 phm of n-butyllithium as an initiator was added to the reactor to initiate the polymerization reaction. 10 minutes after the polymerization temperature reached the maximum temperature, 268 g of butadiene was added to proceed with the polymerization. 5 minutes after the polymerization temperature reached the maximum temperature, 0.04 phm of dichlorodimethylsilane as a coupling agent was added to proceed with the coupling. 15 minutes later, caprylic acid as a polymerization terminator was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the terminated polymerization solution, and cyclohexane was removed using a roll mill to prepare a copolymer.

[0176] Experimental Example 1-1

[0177] The molecular weight, coupling efficiency, and composition of each copolymer manufactured in Examples 1-1 to 1-5 and Comparative Example 1-1 were analyzed using the following method, and the results are shown in Table 1 below.

[0178] 1) Molecular weight analysis

[0179] In the above Examples 1-1 to 1-5, the weight average molecular weight before coupling using KER-950 (Mw before coupling), the weight average molecular weight of the coupled structure formed after coupling (Mw after coupling), and the weight average molecular weight of the entire product (total Mw) were measured, respectively.

[0180] The weight-average molecular weight of each was analyzed using high-performance liquid chromatography (separation module Waters 2690). The analysis was performed under the conditions of column temperature 40°C, THF solvent, and flow rate 1.0 mL / min. The column used was divinylbenzene Styragel HR 5E, HR 4, and HR 2 connected in series, and the refractive index difference was detected using a refractive index detector with a polystyrene standard sample as the standard.

[0181] 2) Coupling efficiency analysis

[0182] The coupling efficiency was analyzed according to Equation 1 below using the area of ​​the polymer peak appearing in GPC (gel permeation chromatography).

[0183] <Formula 1>

[0184] Coupling efficiency (%) = {(area of ​​coupled polymer) / (area of ​​total polymer)} × 100

[0185] 3) Composition analysis

[0186] The styrene content and vinyl content of the butadiene block in the copolymer were analyzed.

[0187] Styrene and vinyl content analysis was performed using a nuclear magnetic resonance spectrometer (Bruker NMR-400), and the samples were analyzed using chloroform-d as a solvent.

[0188] Before coupling Mw (g / mol) After coupling Mw (g / mol) Total Mw (g / mol) Coupling efficiency (%) Styrene content (wt%) Vinyl content (mol%) Example 1-147, 300 119, 700 61, 300 21.73 2.55 9.4 Example 1-251, 700 126, 400 67, 900 23.9 32.55 9.9 Example 1-349, 500 126, 000 65, 400 22.6 32.45 8.2 Example 1-445, 500 113, 500 59, 200 21.9 32.45 6.7 Example 1-545, 300 111, 200 57, 800 20.43 2.35 6.7 Comparative example 1-154,300119,40068,90023.932.163.5

[0189] Manufacturing example

[0190] The copolymers manufactured in the above examples and comparative examples and pure asphalt in a molten state were mixed in a high-speed shear mixer at 180°C for 2 hours to manufacture a modified asphalt composition. The composition ratio of the modified asphalt composition is shown in Table 2 below.

[0191] Classification Pure asphalt copolymer Content (weight parts) Type Content (weight parts) Manufacturing example 1-1100 Example 1-17.5 Manufacturing example 2-1100 Example 1-27.5 Manufacturing example 3-1100 Example 1-37.5 Manufacturing example 4-1100 Example 1-47.5 Manufacturing example 5-1100 Example 1-57.5 Comparative Manufacturing example 1-1100 Comparative example 1-17.5

[0192] Experimental Example 1-2

[0193] The properties of each modified asphalt composition manufactured in Manufacturing Examples 1-1 to 1-5 and Comparative Manufacturing Example 1-1 were measured by the following method, and the results are shown in Table 3 below.

[0194] 1) Softening point: Measured according to ASTM D36.

[0195] 2) Fraass breaking point: Measured according to EN 12593.

[0196] 3) Difference in softening point of phase separation: To evaluate storage stability, the difference in softening point between the top and bottom of the separated composition was measured according to ASTM D7173.

[0197] 4) Rotational viscosity (rotational viscosity @135 ℃): Measured according to ASTM D4402.

[0198] Classification Softening point (℃)Plasma withdrawal point (℃)Phase separation Softening point difference (℃)Rotational viscosity (cps) Manufacturing example 1-186.6-18.717.82300 Manufacturing example 1-290-24.3322775 Manufacturing example 1-388.5-20.719.62475 Manufacturing example 1-487.5-22.319.62150 Manufacturing example 1-587.2-22.015.32100Comparative Manufacturing example 1-182.2-19.123.32725

[0199] Referring to Table 3 above, it was confirmed that the modified asphalt composition of Manufacturing Example 1-1 had a small difference in phase separation softening point compared to the modified asphalt composition of Comparative Manufacturing Example 1-1, thus exhibiting excellent storage stability, a high softening point, thus exhibiting excellent high-temperature characteristics, and a low viscosity.

[0200] The modified asphalt composition of Manufacturing Example 1-2, which was manufactured using the copolymer of Example 1-2 having a higher weight average molecular weight before coupling than that of Example 1-1, had a high softening point and a low foam breaking point, so that both high-temperature and low-temperature properties were excellent, but it was confirmed that the difference in phase separation softening point and viscosity was somewhat high.

[0201] The modified asphalt composition of Manufacturing Example 1-3, manufactured using the copolymer of Example 1-3 in which the amount of divinylbenzene added was doubled compared to Example 1-1, exhibited excellent high-temperature and low-temperature properties, excellent storage stability due to a small difference in phase separation softening point, and low viscosity.

[0202] The modified asphalt composition of Manufacturing Example 1-4, manufactured using the copolymer of Example 1-4 having lower pre-coupling weight average molecular weight and total weight average molecular weight compared to Example 1-3, was confirmed to have excellent high-temperature and low-temperature properties, excellent storage stability due to a small difference in phase separation softening point, and low viscosity.

[0203] The modified asphalt composition of Manufacturing Example 1-5, manufactured using the copolymer of Example 1-5, which had a lower coupling efficiency compared to Example 1-3 by reducing the amount of KER-950 added, was confirmed to have excellent high-temperature and low-temperature properties, a small difference in phase separation softening point, excellent storage stability, and low viscosity.

[0204] Example 2-1

[0205] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of a polar modifier, and 128 g of styrene were injected into the reactor, and the temperature was maintained at 50°C, after which 14 g of butadiene was injected. 0.20 phm of n-butyllithium, an initiator, was injected into the reactor to initiate a polymerization reaction to form a tapered butadiene / styrene block. 10 minutes after the polymerization temperature reached the maximum temperature, 258 g of butadiene was added to proceed with the polymerization. 5 minutes after the polymerization temperature reached the maximum temperature, 0.04 phm of dichlorodimethylsilane, a coupling agent, was added to proceed with the coupling. After 15 minutes, caprylic acid, a polymerization terminator, was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the terminated polymerization solution, and cyclohexane was removed using a roll mill to produce a copolymer.

[0206] Example 2-2

[0207] A copolymer was prepared in the same manner as in Example 2-1, except that 0.13 phm of KER-950 (Kumho P&B Chemical Co., Ltd., CAS No. 30583-72-3) was added as a coupling agent.

[0208] Example 2-3

[0209] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of polar modifier, and 14 g of butadiene were injected into the reactor, and the temperature was maintained at 50°C. 0.20 phm of n-butyllithium, an initiator, was injected into the reactor to initiate the polymerization reaction. Five minutes after the polymerization temperature reached the maximum temperature, 128 g of styrene was injected to form a diblock structure in which butadiene blocks and styrene blocks were combined. 5 minutes after the polymerization temperature reached the maximum temperature, 258 g of butadiene was injected to proceed with the polymerization. Five minutes after the polymerization temperature reached the maximum temperature, 0.04 phm of dichlorodimethylsilane, a coupling agent, was injected to proceed with the coupling. 15 minutes later, caprylic acid, a polymerization terminator, was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the completed polymerization solution, and cyclohexane was removed using a roll mill to prepare a copolymer.

[0210] Example 2-4

[0211] A copolymer was prepared in the same manner as in Example 2-3, except that 0.13 phm of KER-950 (Kumho P&B Chemical Co., Ltd., CAS No. 30583-72-3) was added as a coupling agent.

[0212] Comparative Example 2-1

[0213] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of polar modifier, and 132 g of styrene were injected into the reactor, and the temperature was maintained at 50°C. 0.21 phm of n-butyllithium as an initiator was added to the reactor to initiate the polymerization reaction. 10 minutes after the polymerization temperature reached the maximum temperature, 268 g of butadiene was added to proceed with the polymerization. 5 minutes after the polymerization temperature reached the maximum temperature, 0.04 phm of dichlorodimethylsilane as a coupling agent was added to proceed with the coupling. 15 minutes later, caprylic acid as a polymerization terminator was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the terminated polymerization solution, and cyclohexane was removed using a roll mill to prepare a copolymer.

[0214] Experimental Example 2-1

[0215] The molecular weight, coupling efficiency, and composition of each copolymer manufactured in Examples 2-1 to 2-4 and Comparative Example 2-1 were analyzed in the same manner as in Experimental Example 1-1, and the results are shown in Table 4 below.

[0216] Before coupling Mw (g / mol) After coupling Mw (g / mol) Total Mw (g / mol) Coupling efficiency (%) Styrene content (wt%) Vinyl content (mol%) Example 2-150, 400 111, 900 64, 600 23.13 3.36 1.2 Example 2-249, 200 118, 000 65, 400 23.63 4.26 2.4 Example 2-352, 600 115, 700 67, 600 23.33 3.16 1.0 Example 2-452, 000 119, 500 69, 800 24.7 33.56 0.7 Comparative example 2-154, 300 119, 400 68, 900 23.93 2.16 3.5

[0217] Manufacturing example

[0218] The copolymers manufactured in the above examples and comparative examples and pure asphalt in a molten state were mixed in a high-speed shear mixer at 180°C for 2 hours to manufacture a modified asphalt composition. The composition ratio of the modified asphalt composition is shown in Table 5 below.

[0219] Classification Pure Asphalt Copolymer Content (weight parts) Type Content (weight parts) Manufacturing Example 2-1100 Example 2-17.5 Manufacturing Example 2-2100 Example 2-27.5 Manufacturing Example 2-3100 Example 2-37.5 Manufacturing Example 2-4100 Example 2-47.5 Comparative Manufacturing Example 2-1100 Comparative Example 2-17.5

[0220] Experimental Example 2-2

[0221] The properties of each modified asphalt composition manufactured in Manufacturing Examples 2-1 to 2-4 and Comparative Manufacturing Example 2-1 were measured in the same manner as in Experimental Example 1-2, and the results are shown in Table 6 below.

[0222] Softening point (℃)Plasma withdrawal point (℃)Phase separation softening point difference (℃)Rotational viscosity (cps)Manufacturing example 2-175.8-19.64.82200Manufacturing example 2-277.6-19.42.42100Manufacturing example 2-377.9-17.514.52350Manufacturing example 2-479.8-17.712.52275Comparative manufacturing example 2-182.2-19.123.32725

[0223] Referring to Table 6 above, the modified asphalt compositions of Manufacturing Examples 2-1 and 2-2 have a slightly lower softening point than the modified asphalt composition of Comparative Manufacturing Example 2-1, but have a low powder breaking point, so they have excellent low-temperature characteristics, and the difference in phase separation softening point compared to the modified asphalt composition of Comparative Manufacturing Example 2-1 is very small, so it was confirmed that they have excellent storage stability and low viscosity.

[0224] The modified asphalt compositions of Manufacturing Examples 2-3 and 2-4 had a slightly lower softening point and a slightly higher foam breaking point than the modified asphalt composition of Comparative Manufacturing Example 2-1, but the difference in phase separation softening point was smaller than that of the modified asphalt composition of Comparative Manufacturing Example 2-1, so it was confirmed that they had excellent storage stability and low viscosity.

[0225] Example 3-1

[0226] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of polar modifier, and 132 g of styrene were injected into the reactor, and the temperature was maintained at 50°C. 0.22 phm of n-butyllithium as an initiator was added to the reactor to initiate the polymerization reaction. 10 minutes after the polymerization temperature reached the maximum temperature, 268 g of butadiene was added to proceed with the polymerization. 5 minutes after the polymerization temperature reached the maximum temperature, 0.13 phm of KER-950 (Kumho P&B Chemical Co., Ltd., CAS No. 30583-72-3) as a coupling agent was added to proceed with the coupling. 15 minutes later, caprylic acid as a polymerization terminator was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the completed polymerization solution, and cyclohexane was removed using a roll mill to prepare a copolymer.

[0227] Example 3-2

[0228] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of a polar modifier, and 128 g of styrene were injected into the reactor, and the temperature was maintained at 50°C, after which 14 g of butadiene was injected. 0.20 phm of n-butyllithium as an initiator was injected into the reactor to initiate a polymerization reaction to form a tapered butadiene / styrene block. 10 minutes after the polymerization temperature reached the maximum temperature, 258 g of butadiene was injected to proceed with the polymerization. 5 minutes after the polymerization temperature reached the maximum temperature, 0.13 phm of KER-950 (Kumho P&B Chemical Co., Ltd., CAS No. 30583-72-3) as a coupling agent was injected to proceed with the coupling. After 15 minutes, caprylic acid, a polymerization terminator, was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the terminated polymerization solution, and cyclohexane was removed using a roll mill to produce a copolymer.

[0229] Example 3-3

[0230] The interior of a 5 L pressure reactor was sufficiently purged with nitrogen gas. 2.4 kg of purified cyclohexane, 400 ppm of polar modifier, and 14 g of butadiene were injected into the reactor, and the temperature was maintained at 50°C. 0.20 phm of n-butyllithium, an initiator, was injected into the reactor to initiate the polymerization reaction. Five minutes after the polymerization temperature reached the maximum temperature, 128 g of styrene was injected to form a diblock structure in which butadiene blocks and styrene blocks were combined. 5 minutes after the polymerization temperature reached the maximum temperature, 258 g of butadiene was injected to proceed with the polymerization. 5 minutes after the polymerization temperature reached the maximum temperature, 0.13 phm of KER-950 (Kumho P&B Chemical Co., Ltd., CAS No. 30583-72-3), a coupling agent, was injected to proceed with the coupling. After 15 minutes, caprylic acid, a polymerization terminator, was added to the polymerization solution to completely remove the activity of the living polymer. An antioxidant was added to the terminated polymerization solution, and cyclohexane was removed using a roll mill to produce a copolymer.

[0231] Comparative Example 3-1

[0232] A copolymer was prepared in the same manner as in Example 3-1, except that 0.21 phm of n-butyllithium and 0.04 phm of dichlorodimethylsilane as a coupling agent were added.

[0233] Experimental Example 3-1

[0234] The molecular weight, coupling efficiency, and composition of each copolymer manufactured in Examples 3-1 to 3-3 and Comparative Example 3-1 were analyzed in the same manner as in Experimental Example 1-1, and the results are shown in Table 7 below.

[0235] Before coupling Mw (g / mol) After coupling Mw (g / mol) Total Mw (g / mol) Coupling efficiency (%) Styrene content (wt%) Vinyl content (mol%) Example 3-151, 600 116, 800 65, 300 23.7 32.5 60.6 Example 3-249, 200 118, 000 65, 400 23.6 34.2 62.4 Example 3-352, 000 119, 500 69, 800 24.7 33.5 60.7 Comparative example 3-154, 300 119, 400 68, 900 23.9 32.1 63.5

[0236] Manufacturing example

[0237] The copolymers manufactured in the above examples and comparative examples and pure asphalt in a molten state were mixed in a high-speed shear mixer at 180°C for 2 hours to manufacture a modified asphalt composition. The composition ratio of the modified asphalt composition is shown in Table 8 below.

[0238] Classification Pure Asphalt Copolymer Content (parts by weight) Type Content (parts by weight) Manufacturing Example 3-1100 Example 3-17.5 Manufacturing Example 3-2100 Example 3-27.5 Manufacturing Example 3-3100 Example 3-37.5 Comparative Manufacturing Example 3-1100 Comparative Example 3-17.5

[0239] Experimental Example 3-2

[0240] The properties of each modified asphalt composition manufactured in Manufacturing Examples 3-1 to 3-3 and Comparative Manufacturing Example 3-1 were measured in the same manner as in Experimental Example 1-1, and the results are shown in Table 9 below.

[0241] Distinction Softening point (℃)Plasma withdrawal point (℃)Phase separation softening point difference (℃)Rotational viscosity (cps)Manufacturing example 3-186.1-2022.42325Manufacturing example 3-277.6-19.42100Manufacturing example 3-379.8-17.712.52275Comparative manufacturing example 3-182.2-19.123.32725

[0242] Referring to Table 9 above, it was confirmed that the modified asphalt composition of Manufacturing Example 3-1 had a higher softening point and a lower foam breaking point than the modified asphalt composition of Comparative Manufacturing Example 3-1 using dichlorodimethylsilane as a coupling agent, thereby exhibiting excellent high-temperature and low-temperature properties. In addition, it was confirmed that the difference in phase separation softening point was small, resulting in excellent storage stability, and that the viscosity was lower than that of the modified asphalt composition of Comparative Manufacturing Example 3-1.

[0243] The modified asphalt composition of Manufacturing Example 3-2 has a softening point that is somewhat lower than that of the modified asphalt composition of Comparative Manufacturing Example 3-1, but has a low powder breaking point, so it has excellent low-temperature characteristics. It was confirmed that the difference in phase separation softening point is very small compared to that of the modified asphalt composition of Comparative Manufacturing Example 3-1, so it has excellent storage stability and low viscosity.

[0244] The modified asphalt composition of Manufacturing Example 3-3 had a slightly lower softening point and a slightly higher foam breaking point than the modified asphalt composition of Comparative Manufacturing Example 3-1, but the difference in phase separation softening point was smaller than that of the modified asphalt composition of Comparative Manufacturing Example 3-1, so it was confirmed that the storage stability was excellent and the viscosity was low.

[0245] The description of this specification above is for illustrative purposes only, and those skilled in the art will readily appreciate that aspects of this specification can be readily modified into other specific forms without altering the technical concepts or essential features described herein. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0246] The scope of this specification is indicated by the claims set forth below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included within the scope of this specification.

Claims

1. An additive composition for modified asphalt, comprising a copolymer represented by the following chemical formula 1: <Chemical Formula 1> (A-C-B) n -X In the above chemical formula 1, A is a block composed of aromatic vinyl monomers, B is a block composed of a conjugated diene monomer, C is the first coupling agent, X is a second coupling agent, n is an integer from 2 to 4, The above second coupling agent is a non-aromatic compound having two or more epoxy groups.

2. In paragraph 1, An additive composition for modified asphalt, wherein the first coupling agent is a compound having two or more vinyl groups.

3. In paragraph 1, An additive composition for modified asphalt, wherein the first coupling agent is one selected from the group consisting of divinylnaphthalene, divinylbenzene, 2,5-divinylthiophene, trivinylbenzene, 1,4-divinyloxybenzene, methoxy-substituted divinylbenzene, diisopropenylbenzene, 4-(4-(2-isopropenylphenoxy)butyl)styrene, and combinations of two or more thereof.

4. In paragraph 1, An additive composition for modified asphalt, wherein the second coupling agent is a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups.

5. An additive composition for modified asphalt, comprising a copolymer represented by the following chemical formula 2: <Chemical Formula 2> (D-E) n -Y In the above chemical formula 2, D is a block composed of a conjugated diene monomer and an aromatic vinyl monomer, E is a block composed of conjugated diene monomers, Y is a third coupling agent, n is an integer from 2 to 4.

6. In paragraph 5, An additive composition for modified asphalt, wherein the block composed of the above conjugated diene monomer and aromatic vinyl monomer has a diblock, random or tapered structure.

7. In paragraph 5, An additive composition for modified asphalt, wherein the content of the conjugated diene monomer contained in the block composed of the conjugated diene monomer and the aromatic vinyl monomer is 1 to 10 wt% based on the total weight of the conjugated diene monomer contained in the copolymer.

8. In paragraph 5, The third coupling agent is one selected from the group consisting of dialkyl carbonate, dialkyl malonate, dialkyl phthalate, dialkyl succinate, dialkyl glutarate, dialkyl adipate, dialkyl pimelate, dialkyl suberate, dialkyl sebacate, dialkyl azelate, dialkyl brassylate, dialkyl tetracanedioate, dicarboxylate, tricarboxylate, diester compound, triester compound, tetrachlorosilane, dichlorodimethylsilane, divinylnaphthalene, divinylbenzene, 2,5-divinylthiophene, trivinylbenzene, 1,4-divinyloxybenzene, methoxy-substituted divinylbenzene, diisopropenylbenzene, 4-(4-(2-isopropenylphenoxy)butyl)styrene, and combinations of two or more thereof.

9. In paragraph 5, An additive composition for modified asphalt, wherein the third coupling agent is a non-aromatic compound having two or more epoxy groups.

10. An additive composition for modified asphalt, comprising a copolymer represented by the following chemical formula 3: <Chemical Formula 3> (F-G) n -Z In the above chemical formula 3, F is a block containing an aromatic vinyl monomer, G is a block composed of conjugated diene monomers, Z is the fourth coupling agent, n is an integer from 2 to 4, The above fourth coupling agent is a non-aromatic compound having two or more epoxy groups.

11. In paragraph 10, An additive composition for modified asphalt, wherein the block comprising the aromatic vinyl monomer is a block composed of an aromatic vinyl monomer; or a block composed of an aromatic vinyl monomer and a conjugated diene monomer.

12. In paragraph 11, An additive composition for modified asphalt, wherein the block composed of the above aromatic vinyl monomer and conjugated diene monomer has a diblock, random or tapered structure.

13. In paragraph 10, An additive composition for modified asphalt, wherein the fourth coupling agent is a non-aromatic compound having two or more epoxy groups and one or more halogenated alkyl groups.

14. In any one of paragraphs 1, 5 and 10, An additive composition for modified asphalt, wherein the content of aromatic vinyl monomer in the above copolymer is 10 to 60 wt%.

15. In any one of paragraphs 1, 5 and 10, An additive composition for modified asphalt, wherein the vinyl content of the block composed of the above conjugated diene monomer is 10 to 80 mol%.

16. In any one of paragraphs 1, 5 and 10, An additive composition for modified asphalt, wherein the weight average molecular weight (Mw) of the copolymer is 20,000 to 1,000,000 g / mol.

17. Asphalt; and A modified asphalt composition comprising an additive composition for modified asphalt according to any one of claims 1, 5 and 10.

18. In paragraph 17, A modified asphalt composition, wherein the content of the additive composition for modified asphalt is 0.5 to 40 parts by weight based on 100 parts by weight of the above asphalt.