KR102251010B1 - Block copolymer compositon, method for preparing the composition and asphalt composition comprising the composition - Google Patents

Abstract

The present invention relates to a block copolymer composition, and more particularly, a first block copolymer comprising a repeating unit block derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene-based monomer exceeding 80% by weight to 99% by weight % Below; And a second block copolymer including a repeating unit block derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer, including 1% by weight or more to less than 20% by weight, and the total of the first block copolymer With respect to the content, the content of the repeating unit block derived from the first aromatic vinyl monomer is 20% by weight or more to less than 35% by weight, and the content of the vinyl group is 5% by weight based on the total content of the repeating unit block derived from the first conjugated diene-based monomer. % Or more to less than 25% by weight, and based on the total content of the second block copolymer, the content of the repeating unit block derived from the second aromatic vinyl monomer is 35% to 50% by weight, and the second conjugated diene-based monomer It provides a block copolymer composition having a vinyl group content of 25% to 50% by weight based on the total content of the derived repeating unit block, a method for preparing the same, and an asphalt composition including the same.

Description

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

The present invention relates to a block copolymer composition, and more particularly, to a block copolymer composition for use as an asphalt modifier, a method for preparing the same, and an asphalt composition comprising the same.

Asphalt is a residue after most of the volatile oil components of petroleum crude oil evaporate, and maintains a highly viscous liquid or semi-solid state at high temperatures, but has properties that harden at temperatures below room temperature. In addition, asphalt is widely applied to building materials such as road paving materials and waterproofing materials because asphalt is rich in plasticity, has high waterproofing, electrical insulation, adhesiveness, and chemically stable characteristics. However, when such 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 solve this problem, studies to improve the properties of asphalt by adding various polymers have recently been conducted.

For example, there is a method of using an aromatic vinyl hydrocarbon-conjugated diene block copolymer such as a styrene-butadiene-styrene (SBS) block copolymer as a modifier or impact modifier to improve the physical properties of the asphalt composition. However, in the SBS block copolymer of the same molecular weight, the higher the content of the styrene block in the SBS block copolymer of the same molecular weight, the better the softening point, but the solubility is low, the compatibility with asphalt decreases, and physical properties such as low temperature elongation decrease. In the SBS block copolymer of the same molecular weight, the higher the content of the vinyl group is, the better the solubility is, but there is a problem that the storage stability is lowered.

In order to solve such a problem, a method of adjusting the molecular weight of the SBS block copolymer, changing the molecular microstructure of the block copolymer to add a coupling effect, or adding an additive such as oil as a processing aid. Although a method or the like has been proposed, there is a limit to simultaneously improving the softening point, solubility, and low-temperature elongation, which are in a trade-off relationship with each other.

KR 0711270 B1

The problem to be solved in the present invention is, in order to solve the problems mentioned in the technology behind the background of the invention, in applying the block copolymer as an asphalt modifier, the solubility of the block copolymer composition in a trade-off relationship, the asphalt composition It is to improve the low temperature elongation, high temperature viscosity, and softening point of the at the same time.

That is, the present invention was devised to solve the problems of the prior art, and provides a block copolymer composition that can be used as an asphalt modifier, and when the asphalt is modified using the block copolymer composition, the block copolymer composition It is an object of the present invention to provide an asphalt composition in which the solubility, low-temperature elongation and high-temperature viscosity of the asphalt composition are improved to the same level or higher, and the softening point is remarkably improved.

According to an embodiment of the present invention for solving the above problems, the present invention is 80% by weight of a first block copolymer comprising a repeating unit block derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene-based monomer. Greater than or equal to 99% by weight; And a second block copolymer including a repeating unit block derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer, including 1% by weight or more to less than 20% by weight, and the total of the first block copolymer The content of the repeating unit block derived from the first aromatic vinyl monomer is 20% by weight or more to less than 35% by weight, and the content of the vinyl group is 5% by weight based on the total content of the repeating unit block derived from the first conjugated diene-based monomer. The content of the second aromatic vinyl monomer-derived repeating unit block is 35 to 50% by weight, based on the total content of the second block copolymer, and the second conjugated diene-based monomer-derived repeat The content of vinyl groups with respect to the total content of the unit block It provides a block copolymer composition of 25% to 50% by weight.

In addition, the present invention comprises the steps of preparing a first block copolymer comprising a repeating unit derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene-based monomer in a hydrocarbon solvent (S10); In a hydrocarbon solvent, preparing a second block copolymer comprising a repeating unit derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer (S20); And mixing more than 80% by weight to less than 99% by weight of the first block copolymer prepared in step (S10) and 1% by weight to less than 20% by weight of the second block copolymer prepared in step (S20) Including step (S30), the content of the repeating unit block derived from the first aromatic vinyl monomer relative to the total content of the first block copolymer prepared in step (S10) is 20% by weight or more to less than 35% by weight, With respect to the total content of the repeating unit block derived from the first conjugated diene-based monomer, the content of the vinyl group is 5% by weight or more to less than 25% by weight, and with respect to the total content of the second block copolymer prepared in step (S20), the The content of the repeating unit block derived from the second aromatic vinyl monomer is 35% to 50% by weight, and the content of the vinyl group is 25% to 50% by weight based on the total content of the repeating unit block derived from the second conjugated diene-based monomer. It provides a method for preparing a copolymer composition.

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

When using the block copolymer composition according to the present invention as an asphalt modifier, there is an effect of remarkably improving the softening point while improving the solubility of the block copolymer composition, the low-temperature elongation and high-temperature viscosity of the asphalt composition to equal or higher levels.

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

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

In the present invention, the terms'derived repeating unit' and'derived linking group' may refer to a component, structure, or the substance itself originated from a substance, and as a specific example, the'derived repeating unit' is a monomer that is introduced during polymerization of a polymer. It may mean a repeating unit formed in the polymer by participating in the polymerization reaction, and the'derived linking group' refers to each polymer in the coupled polymer by participating in the coupling reaction during the coupling reaction between polymers. It may mean a connector that connects.

In the present invention, the term'block' may refer to a group of repeating units composed of only repeating units derived from the same monomer by participating in the polymerization reaction of only the same monomer in the copolymer. As a specific example, the repeating unit block derived from an aromatic vinyl monomer is aromatic It may mean a block formed of only repeating units derived from a vinyl monomer, and the repeating unit block derived from a conjugated diene-based monomer may mean a block formed only of repeating units derived from a conjugated diene-based monomer.

The block copolymer composition according to the present invention includes a first block copolymer comprising a repeating unit block derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene monomer; And a second block copolymer including a repeating unit block derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer, including 1% by weight or more to less than 20% by weight, and the total of the first block copolymer With respect to the content, the content of the repeating unit block derived from the first aromatic vinyl monomer is 20% by weight or more to less than 35% by weight, and the content of the vinyl group is 5% by weight based on the total content of the repeating unit block derived from the first conjugated diene-based monomer. % Or more to less than 25% by weight, and based on the total content of the second block copolymer, the content of the repeating unit block derived from the second aromatic vinyl monomer is 35% to 50% by weight, and the second conjugated diene-based monomer With respect to the total content of the derived repeating unit block, the content of vinyl group is It may be from 25% by weight to 50% by weight.

In general, in the aromatic vinyl hydrocarbon-conjugated diene block copolymer mainly used as an asphalt modifier, in particular, in the styrene-butadiene-styrene (SBS) triblock copolymer, the content between the styrene block and the butadiene block, the vinyl present in the conjugated diene block Factors related to the microstructure of the molecule, such as the content of groups, are correlated with each other.As the high-temperature properties increase, the low-temperature properties decrease, the increase in the dissolution rate decreases the mechanical properties, and the gel is formed in the asphalt composition during sulfur crosslinking. Such problems may occur. However, the block copolymer composition according to the present invention simultaneously includes heterogeneous block copolymers having different content of repeating unit blocks derived from aromatic vinyl monomers and a content of vinyl groups, so that the solubility of the block copolymer composition and the asphalt composition While improving the low-temperature elongation and high-temperature viscosity to equal or higher levels, there is an effect of remarkably improving the softening point. This is, compared to simply using a block copolymer having an increased content of repeating units derived from an aromatic vinyl monomer when manufacturing an asphalt composition, while preventing physical properties such as solubility and low-temperature elongation from deteriorating, it is derived from an aromatic vinyl monomer having a higher content than the first block copolymer. It may be due to the improvement of the softening point by the second block copolymer containing the repeating unit.

According to an embodiment of the present invention, the first block copolymer may include a repeating unit block derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene-based monomer, and as a specific example, the first aromatic vinyl It may include a repeating unit block derived from a monomer, a repeating unit block derived from a first conjugated diene-based monomer, and a linking group derived from the first coupling agent.

According to an embodiment of the present invention, the repeating unit block derived from the first aromatic vinyl monomer of the first block copolymer may be a block formed by polymerization of the first aromatic vinyl monomer, and the repeating unit derived from the first aromatic vinyl monomer The first aromatic vinyl monomer for forming the unit block is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p- It may be one or more selected from the group consisting of methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene.

In addition, according to an embodiment of the present invention, the repeating unit block derived from the first conjugated diene-based monomer of the first block copolymer may be a block formed by polymerization of the first conjugated diene-based monomer, and the first conjugated The first conjugated diene-based monomer for forming a repeating unit block derived from a diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, It may be one or more selected from the group consisting of isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means a halogen atom).

According to an embodiment of the present invention, when the first block copolymer includes a linking group derived from a first coupling agent in addition to the repeating unit block derived from the first aromatic vinyl monomer and the repeating unit block derived from the first conjugated diene-based monomer, The first coupling agent-derived linking group may be a linking group for connecting a plurality of repeating unit blocks derived from the first conjugated diene-based monomer, and the first coupling agent for forming the linking group derived from the first coupling agent is a vinyl group-containing hydrocarbon-based compound , Ester-based compounds, silane-based compounds, polysiloxane-based compounds, and polyketones may be one or more selected from the group consisting of, a specific example, the first coupling agent as a polyfunctional coupling agent, a vinyl group-containing hydrocarbon-based such as divinylbenzene, etc. compound; Ester compounds such as diethyl adipate and glycidyl methacrylate; Silane compounds such as dimethyldichlorosilane, methyldichlorosilane, methoxysilane, glycidoxy trimethoxysilane, and oxydipropyl bis(trimethoxysilane); polysiloxane compounds such as α,ω-bis(2-trichlorosilylethyl)polydimethylsiloxane, etc.; Or it may be one or more selected from the group consisting of polyketones and the like.

According to an embodiment of the present invention, in the first block copolymer, the content of the repeating unit block derived from the first aromatic vinyl monomer is 20% by weight or more to less than 35% by weight based on the total content of the first block copolymer. , 25% to 33% by weight, or 28% to 31% by weight, and the content of the vinyl group is 5% by weight or more to less than 25% by weight, 10% to 20% by weight, or 13% by weight based on the total content of the repeating unit block derived from the first conjugated diene-based monomer % To 17% by weight, and when the content of the repeating unit block derived from the first aromatic vinyl monomer and the content of the vinyl group in the repeating unit block derived from the first conjugated diene-based monomer are simultaneously satisfied, the block copolymer according to the present invention There is an excellent effect of high temperature viscosity including solubility and low temperature elongation of an asphalt composition comprising the composition as an asphalt modifier.

In addition, according to an embodiment of the present invention, the second block copolymer may include a repeating unit block derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer. It may include a repeating unit block derived from an aromatic vinyl monomer, a repeating unit block derived from a second conjugated diene-based monomer, and a linking group derived from a second coupling agent.

According to an embodiment of the present invention, the repeating unit block derived from the second aromatic vinyl monomer of the second block copolymer may be a block formed by polymerization of the second aromatic vinyl monomer, and the repeating unit derived from the second aromatic vinyl monomer The second aromatic vinyl monomer for forming the unit block is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p -Methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene may be one or more selected from the group consisting of, and may be the same or different from the first aromatic vinyl monomer described above.

In addition, according to an embodiment of the present invention, the repeating unit block derived from the second conjugated diene-based monomer of the second block copolymer may be a block formed by polymerization of the second conjugated diene-based monomer, and the second conjugated The second conjugated diene-based monomer for forming a repeating unit block derived from a diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, It may be one or more selected from the group consisting of isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means a halogen atom), and the first conjugated diene-based monomer described above It may be the same as or different from.

According to an embodiment of the present invention, when the second block copolymer includes a linking group derived from a second coupling agent in addition to the repeating unit block derived from the second aromatic vinyl monomer and the repeating unit block derived from the second conjugated diene-based monomer, The second coupling agent-derived linking group may be a linking group for connecting a plurality of second conjugated diene-based monomer-derived repeating unit blocks, and the second coupling agent for forming the second coupling agent-derived linking group is a vinyl group-containing hydrocarbon-based compound , Ester-based compounds, silane-based compounds, polysiloxane-based compounds, and polyketones may be one or more selected from the group consisting of, a specific example, the first coupling agent as a polyfunctional coupling agent, a vinyl group-containing hydrocarbon-based such as divinylbenzene, etc. compound; Ester compounds such as diethyl adipate and glycidyl methacrylate; Silane compounds such as dimethyldichlorosilane, methyldichlorosilane, methoxysilane, glycidoxy trimethoxysilane, and oxydipropyl bis(trimethoxysilane); polysiloxane compounds such as α,ω-bis(2-trichlorosilylethyl)polydimethylsiloxane, etc.; Alternatively, it may be one or more selected from the group consisting of polyketones, and the like, and may be the same as or different from the first coupling agent described above.

According to an embodiment of the present invention, in the second block copolymer, the content of the repeating unit block derived from the second aromatic vinyl monomer is 35% to 50% by weight, based on the total content of the second block copolymer. Wt% to 47 wt%, or 35% to 45% by weight, and the content of the vinyl group is from 25% to 50% by weight, from 25% to 47% by weight, or from 25% by weight to the total content of the repeating unit block derived from the second conjugated diene-based monomer. It may be 45% by weight, and when the content of the repeating unit block derived from the second aromatic vinyl monomer and the content of the vinyl group in the repeating unit block derived from the second conjugated diene-based monomer are simultaneously satisfied, the block copolymer composition according to the present invention There is an effect of increasing the softening point while maintaining the solubility and low-temperature elongation of the asphalt composition included as an asphalt modifier at equal or higher levels.

That is, according to an embodiment of the present invention, the block copolymer composition comprises a first block copolymer and a second block copolymer having different contents of repeating unit blocks derived from aromatic vinyl monomers and different contents of vinyl groups. It can be included at the same time. As described above, when the content of the repeating unit blocks derived from different aromatic vinyl monomers and the first block copolymer and the second block copolymer each having a different content of vinyl groups are simultaneously included, from the first block copolymer, the present invention In addition to the solubility and low-temperature elongation of the asphalt composition including the block copolymer composition according to the asphalt modifier, it is possible to improve the high-temperature viscosity, and from the second block copolymer, there is an effect of increasing the softening point.

On the other hand, according to an embodiment of the present invention, based on the total content of the block copolymer composition, the content of the first block copolymer is more than 80% by weight to 99% by weight or less, 85% to 98% by weight, or 85 The content of the second block copolymer may be 1% by weight or more to less than 20% by weight, 2% by weight to 15% by weight, or 3% by weight to 15% by weight. Within the range, there is an effect of increasing the softening point while maintaining the solubility and low-temperature elongation of an asphalt composition comprising the block copolymer composition according to the present invention as an asphalt modifier at equal or higher levels.

Further, according to the present invention, a method for preparing the block copolymer composition is provided. The method for preparing a block copolymer composition according to an embodiment of the present invention comprises preparing a first block copolymer comprising a repeating unit derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene monomer in a hydrocarbon solvent. Step S10; In a hydrocarbon solvent, preparing a second block copolymer comprising a repeating unit derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer (S20); And mixing more than 80% by weight to less than 99% by weight of the first block copolymer prepared in step (S10) and 1% by weight to less than 20% by weight of the second block copolymer prepared in step (S20) Including step (S30), the content of the repeating unit block derived from the first aromatic vinyl monomer relative to the total content of the first block copolymer prepared in step (S10) is 20% by weight or more to less than 35% by weight, With respect to the total content of the repeating unit block derived from the first conjugated diene-based monomer, the content of the vinyl group is 5% by weight or more to less than 25% by weight, and with respect to the total content of the second block copolymer prepared in step (S20), the The content of the repeating unit block derived from the second aromatic vinyl monomer is 35% to 50% by weight, and the content of the vinyl group is 25% to 50% by weight based on the total content of the repeating unit block derived from the second conjugated diene-based monomer. I can.

According to an embodiment of the present invention, the step (S10) may be a step for preparing a first solution containing a first block copolymer, and as a specific example, in a hydrocarbon-based solvent, in the presence of a first polymerization initiator , Adding and polymerizing a first aromatic vinyl monomer to prepare a first monoblock polymer solution comprising a polymer for forming a repeating unit block derived from the first aromatic vinyl monomer (S11); To the polymer solution for forming a repeating unit block derived from the first aromatic vinyl monomer prepared in step (S11), a first conjugated diene-based monomer was added and polymerized, and the repeating unit block derived from the first aromatic vinyl monomer and the first conjugated diene-based Preparing a first diblock copolymer solution including a first diblock copolymer including a monomer-derived repeating unit block (S12); And a repeating unit block derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene-based monomer by adding a first coupling agent to the first diblock copolymer solution prepared in step (S12) and performing a coupling reaction. And preparing a first solution including a first block copolymer including a first coupling agent-derived linking group (S13).

According to an embodiment of the present invention, the step (S11) is derived from a first aromatic vinyl monomer for forming a block including a repeating unit derived from the first aromatic vinyl monomer by initiating polymerization when the first block copolymer is polymerized. It may be a step for preparing a first monoblock polymer solution containing a polymer for forming a repeating unit block, and the first monoblock polymer solution prepared in step (S11) is for forming a repeating unit block derived from a first aromatic vinyl monomer. It may include a polymer.

In addition, according to an embodiment of the present invention, in the (S12) step, in the presence of a polymer for forming a repeating unit block derived from the first aromatic vinyl monomer contained in the first monoblock polymer solution prepared in step (S11), A first diblock copolymer comprising a first diblock copolymer comprising a repeating unit block derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene monomer by adding and polymerizing a first conjugated diene monomer It may be a step for preparing a solution. The first monoblock polymer solution prepared in step (S11) contains a polymer for forming a repeating unit block derived from a first aromatic vinyl monomer, and this is a living in which the end of the polymer is in an anionic active state by the polymerization of the previous step (S11). Since it is an anionic polymer, the step (S12) can be carried out without the addition of a separate polymerization initiator. That is, in the step (S12), the polymerization reaction of the first conjugated diene-based monomer additionally added from the living anionic polymer is performed, followed by the repeating unit block derived from the first aromatic vinyl monomer, and then the first added in step (S12). 1 It may be a step for preparing a first diblock copolymer in which a block according to a conjugated diene-based monomer is formed.

In addition, according to an embodiment of the present invention, in the step (S13), the first diblock copolymer contained in the first diblock copolymer solution prepared in the step (S12) is used as a first coupling agent. It may be a step for preparing a first solution including a triblock copolymer coupled with a diblock copolymer, that is, a first block copolymer by a coupling reaction. The first diblock copolymer solution prepared in step (S12) contains a first diblock copolymer, which is derived from the end of the copolymer, specifically, the first conjugated diene-based monomer by polymerization in the preceding step (S12). Since the end of the repeating unit block is a living anionic copolymer in an anionic active state, depending on the number of substituted or addable functional groups contained in the first coupling agent, the functional group of the first coupling agent is the living anion copolymer. A coupling reaction in which the living anionic copolymer is added to the functional group of the first coupling agent or substituted by a coalescence may be performed. That is, in the first block copolymer, the first diblock copolymer may be connected by the first coupling agent according to the number of substituted or addable functional groups contained in the first coupling agent. The first diblock copolymer may be coupled by a linker derived from the first coupling agent, and a more specific example is 2 to 4 first diblock copolymers coupled by a linker derived from the first coupling agent. It may have been.

According to an embodiment of the present invention, the content of the first aromatic vinyl monomer added in the step (S11) is 20% by weight or more to 35% by weight based on the total content of the first aromatic vinyl monomer and the first conjugated diene-based monomer. %, 25 wt% to 33 wt%, or 28 wt% to 31 wt%, and the content of the first conjugated diene-based monomer added in step (S12) is, the first aromatic vinyl monomer and the first conjugated Based on the total content of the diene-based monomer, 65% by weight or more to less than 80% by weight, 67% by weight to 75% by weight, or 69% by weight to 72% by weight, within this range, by the method for preparing the block copolymer The solubility and low-temperature elongation of an asphalt composition comprising the prepared block copolymer composition as an asphalt modifier has excellent effects in high temperature viscosity.

According to an embodiment of the present invention, in the first block copolymer prepared in step (S10), the content of the repeating unit block derived from the first aromatic vinyl monomer is 20 with respect to the total content of the first block copolymer. Wt% or more to less than 35 wt%, 25 wt% to 33 wt%, or 28 wt% to 31 wt%, and the content of the vinyl group in the first block copolymer is 5 wt% or more to less than 25 wt%, 10 Wt% to 20 wt%, or It may be 13% to 17% by weight, and when the content of the repeating unit block derived from the first aromatic vinyl monomer and the content of the vinyl group in the first block copolymer are simultaneously satisfied, the block copolymer composition according to the present invention is used as asphalt. There is an excellent effect of high temperature viscosity including solubility and low temperature elongation of the asphalt composition included as a modifier.

In addition, according to an embodiment of the present invention, the (S10) step, after the coupling reaction of the step (S13), selectively removes the activity of the active polymer by adding water or alcohol to the reactor. It may contain more.

In addition, according to an embodiment of the present invention, the step (S20) may be a step for preparing a second solution containing the second block copolymer, and may be performed separately from the step (S10), It may be performed simultaneously or sequentially with step (S10). The step (S20) is a specific example, in a hydrocarbon-based solvent, in the presence of a second polymerization initiator, by adding and polymerizing a second aromatic vinyl monomer, the second comprising a polymer for forming a repeating unit block derived from the second aromatic vinyl monomer. Preparing a monoblock polymer solution (S21); To the polymer solution for forming a repeating unit block derived from the second aromatic vinyl monomer prepared in step (S21), a second conjugated diene-based monomer was added and polymerized, and the repeating unit block derived from the second aromatic vinyl monomer and the second conjugated diene-based Preparing a second diblock copolymer solution including a second diblock copolymer including a monomer-derived repeating unit block (S22); And by adding a second coupling agent to the second diblock copolymer solution prepared in step (S22) and performing a coupling reaction, a repeating unit block derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer. And preparing a second solution including a second block copolymer including a second coupling agent-derived linking group (S23).

According to an embodiment of the present invention, the step (S21) is derived from a second aromatic vinyl monomer for forming a block including a repeating unit derived from the second aromatic vinyl monomer by initiating polymerization when the second block copolymer is polymerized. It may be a step for preparing a second monoblock polymer solution containing a polymer for forming a repeating unit block, and the second monoblock polymer solution prepared in step (S21) is for forming a repeating unit block derived from a second aromatic vinyl monomer. It may include a polymer.

In addition, according to an embodiment of the present invention, the step (S22) is in the presence of a polymer for forming a repeating unit block derived from the second aromatic vinyl monomer contained in the second monoblock polymer solution prepared in step (S21), A second diblock copolymer comprising a second diblock copolymer comprising a repeating unit block derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene monomer by adding and polymerizing a second conjugated diene monomer It may be a step for preparing a solution. The second monoblock polymer solution prepared in step (S21) contains a polymer for forming a repeating unit block derived from a second aromatic vinyl monomer, and this is a living in which the end of the polymer is in anionic active state by the polymerization of the previous step (S21). Since it is an anionic polymer, the step (S22) can be carried out without the addition of a separate polymerization initiator. That is, in the step (S22), a polymerization reaction of the second conjugated diene-based monomer additionally added from the living anionic polymer is carried out, followed by the repeating unit block derived from the second aromatic vinyl monomer, and the second added in step (S22). 2 It may be a step for preparing a second diblock copolymer in which a block according to the conjugated diene-based monomer is formed.

In addition, according to an embodiment of the present invention, in the step (S23), the second diblock copolymer contained in the second diblock copolymer solution prepared in the step (S22) is used as a second coupling agent. It may be a step for preparing a second solution including a triblock copolymer coupled with a diblock copolymer, that is, a second block copolymer by performing a coupling reaction. The second diblock copolymer solution prepared in step (S22) contains a second diblock copolymer, which is derived from the end of the copolymer, specifically, a second conjugated diene-based monomer by polymerization in the preceding step (S22). Since the end of the repeating unit block is a living anionic copolymer in an anionic active state, depending on the number of functional groups that can be substituted or added contained in the second coupling agent, the functional group of the second coupling agent is the living anion copolymer. A coupling reaction in which the living anionic copolymer is added to the functional group of the second coupling agent or substituted by a coalescence may be performed. That is, the second block copolymer may be one in which the second diblock copolymer is connected by the second coupling agent according to the number of substituted or addable functional groups contained in the second coupling agent. The second diblock copolymer may be coupled by a linker derived from the second coupling agent, and a more specific example is 2 to 4 second diblock copolymers coupled by a linker derived from the second coupling agent. It may have been.

According to an embodiment of the present invention, the content of the second aromatic vinyl monomer added in the step (S21) is 35% to 50% by weight based on the total content of the first aromatic vinyl monomer and the first conjugated diene-based monomer. , 35% by weight to 47% by weight, or 35% by weight to 45% by weight, and the content of the second conjugated diene-based monomer added in step (S22) is, the second aromatic vinyl monomer and the second conjugated diene-based monomer Based on the total monomer content, it may be 50% to 65% by weight, 53% to 65% by weight, or 55% to 65% by weight, and within this range, the block copolymer prepared by the method for preparing the block copolymer There is an effect of increasing the softening point while maintaining the solubility and low-temperature elongation of an asphalt composition comprising the coalescence composition as an asphalt modifier at equal or higher levels.

According to an embodiment of the present invention, in the second block copolymer prepared in step (S20), the content of the repeating unit block derived from the second aromatic vinyl monomer is 35 with respect to the total content of the second block copolymer. Wt% to 50 wt%, 35 wt% to 47 wt%, or 35 wt% to 45 wt%, and the content of the vinyl group in the second block copolymer is 25 wt% to 50 wt%, 25 wt% to 47 When the content of the repeating unit block derived from the second aromatic vinyl monomer and the content of the vinyl group in the second block copolymer are satisfied at the same time, the block copolymer according to the present invention There is an effect of increasing the softening point while maintaining the solubility and low-temperature elongation of an asphalt composition comprising the coalescence composition as an asphalt modifier at equal or higher levels.

In addition, according to an embodiment of the present invention, the (S20) step, after the coupling reaction of the step (S23), selectively removes the activity of the active polymer by adding water or alcohol to the reactor. It may contain more.

Meanwhile, according to an embodiment of the present invention, the first aromatic vinyl monomer, the second aromatic vinyl monomer, the first conjugated diene monomer, the second conjugated diene monomer, and the first couple described in the method for preparing the block copolymer composition. The ring agent and the second coupling agent may be the same as the monomer and coupling agent described above.

According to an embodiment of the present invention, in the first monoblock polymer solution, the second monoblock polymer solution, the first diblock copolymer solution, the second diblock copolymer solution, the first solution and the second solution, ' The'solution' may mean containing a polymer, a diblock copolymer, and a block copolymer produced by the polymerization or coupling reaction of each step described above in a dispersed or dissolved form in a hydrocarbon-based solvent.

According to an embodiment of the present invention, the hydrocarbon-based solvent does not react with a polymerization initiator, and can be used as long as it is usually used for anionic polymerization reaction, and specific examples are butane, n-pentane, n-hexane, n-heptane or iso -Linear or branched aliphatic hydrocarbon compounds such as octane; Cyclic aliphatic hydrocarbon compounds unsubstituted or substituted with an alkyl group such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane or methyl cycloheptane; And an aromatic hydrocarbon compound unsubstituted or substituted with an alkyl group such as benzene, toluene, xylene or naphthalene, and any one of them or a mixture of two or more thereof may be used.

In addition, according to an embodiment of the present invention, the first polymerization initiator and the second polymerization initiator may each independently be an organometallic compound, and the (S11) and (S21) steps are derived from the organometallic compound. It can be carried out by anionic polymerization reaction by the anion. As a specific example, the organometallic compound may be an organic lithium compound, and specific examples are n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allyllithium, vinyl It may be one or more selected from the group consisting of lithium, phenyllithium, and benzyllithium.

According to an embodiment of the present invention, in the step (S30), the first block copolymer and the second block copolymer are mixed or blended with each other, so that the first block copolymer and the second block copolymer are mixed with each other. It may be a step for preparing a block copolymer composition that is present in the state. The mixing of step (S30) may be carried out by mixing the first block copolymer prepared in step (S10) and the second block copolymer prepared in step (S20) in the form of powder, respectively, and block In order to evenly disperse and distribute the first block copolymer and the second block copolymer in the copolymer composition, a first solution containing the first block copolymer prepared in step (S10), and the step (S20) It can be carried out by mixing the second solution containing the second block copolymer prepared in, in this case, the first block copolymer and the second block copolymer have excellent dispersibility and even distribution, and block copolymerization There is an excellent effect in the balance between the physical properties of the asphalt composition containing the coalescence.

In addition, according to an embodiment of the present invention, when mixing in the step (S30), the content of the first block copolymer is greater than 80% by weight to 99% by weight or less, 85% by weight, based on the total content of the block copolymer composition. % To 98% by weight, or 85% to 97% by weight, and the content of the second block copolymer is 1% by weight or more to less than 20% by weight, 2% by weight to 15% by weight, or 3% by weight to It may be 15% by weight, and within this range, the second block copolymer is evenly dispersed using the first block copolymer as a matrix, and accordingly, the block copolymer composition prepared by the method for preparing the block copolymer composition is used as an asphalt modifier. There is an effect of increasing the softening point while maintaining the solubility and low-temperature elongation of the asphalt composition included as at equal or higher levels. Meanwhile, according to an embodiment of the present invention, when the mixing of the step (S30) is performed by mixing the first solution and the second solution, the content of the first block copolymer and the second block copolymer is solid content. It may be a reference content.

In addition, according to the present invention, there is provided an asphalt composition comprising the block copolymer composition as an asphalt modifier. The asphalt composition may include the block copolymer composition and asphalt. At this time, the block copolymer composition may be included in 1% to 10% by weight, 3% to 8% by weight, or 4% to 6% by weight based on the total content of the asphalt composition, within this range The copolymer composition has excellent solubility in asphalt and has excellent properties of the asphalt composition.

According to an embodiment of the present invention, the asphalt composition may further include a crosslinking agent for crosslinking the asphalt composition. The crosslinking agent may be a sulfur compound containing sulfur or iron sulfate, and a specific example may be elemental sulfur (powder), and the crosslinking agent may be included in an amount of 0.05% to 3% by weight based on the total content of the asphalt composition. By maintaining an appropriate crosslinking reaction within the range, there is an effect of improving high-temperature physical properties and elasticity, and preventing gelation.

In addition, according to an embodiment of the present invention, the asphalt may include asphaltene in an amount of 1% to 40% by weight, or 5% to 30% by weight based on the total weight of the asphalt.

In addition, according to an embodiment of the present invention, the asphalt composition may be a road paving material or a building material such as a waterproof material.

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

Manufacturing example

Manufacturing Example 1

4,593 g of purified cyclohexane and 264 g of styrene were added to a 10 L reactor substituted with nitrogen, and the temperature was raised to 60°C while stirring. When the reactor temperature reached 60° C., 28.5 g of n-butyllithium was added to the reactor to polymerize the styrene block.

Subsequently, 616 g of 1,3-butadiene was added to the mixed solution in which the styrene block was produced, under conditions of 65° C. and 1.0 bar, and polymerized until the 1,3-butadiene was completely consumed (styrene)-(butadiene. ) A diblock copolymer was prepared.

After completion of the polymerization reaction, 0.85 g of dimethyldichlorosilane as a coupling agent was added to the mixed solution in which the (styrene)-(butadiene) diblock copolymer was produced, under conditions of 105° C. and 3.5 bar, followed by a coupling reaction for 5 minutes. Was carried out. Subsequently, 1 g of water was added as a reaction terminator to remove the reaction activity, and then a polymer solution containing a block copolymer (SBS A) to which a (styrene)-(butadiene) diblock copolymer was coupled was prepared.

Manufacturing Example 2

In Preparation Example 1, the preparation above except that 352 g of styrene and 0.59 g of ditetrahydrofurylpropane (DTHFP) were added instead of 264 g of styrene, and 528 g of 1,3-butadiene was added instead of 616 g. In the same manner as in Example 1, a polymer solution containing a block copolymer (SBS B) to which a (styrene)-(butadiene) diblock copolymer is coupled was prepared.

Manufacturing Example 3

In Preparation Example 1, the preparation above except that 326 g of styrene and 0.59 g of ditetrahydrofurylpropane (DTHFP) were added instead of 264 g of styrene, and 555 g of 1,3-butadiene was added instead of 616 g. In the same manner as in Example 1, a polymer solution containing a block copolymer (SBS C) to which a (styrene)-(butadiene) diblock copolymer is coupled was prepared.

Manufacturing Example 4

In Preparation Example 1, 352 g was added instead of 264 g of styrene, and 528 g of 1,3-butadiene was added instead of 616 g. A polymer solution containing a block copolymer (SBS D) to which a butadiene) diblock copolymer is coupled was prepared.

Manufacturing Example 5

In Preparation Example 1, it was carried out in the same manner as in Preparation Example 1, except that 326 g of styrene was added instead of 264 g, and 555 g of 1,3-butadiene was added instead of 616 g, and (styrene)-( A polymer solution containing a block copolymer (SBS E) to which a butadiene) diblock copolymer is coupled was prepared.

Manufacturing Example 6

In Preparation Example 1, the preparation above except that 528 g of styrene and 0.59 g of ditetrahydrofurylpropane (DTHFP) were added instead of 264 g of styrene, and 352 g of 1,3-butadiene was added instead of 616 g. In the same manner as in Example 1, a polymer solution containing a block copolymer (SBS F) to which a (styrene)-(butadiene) diblock copolymer is coupled was prepared.

Example

Example 1

95 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 5 parts by weight of the SBS B solution prepared in Preparation Example 2 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Example 2

90 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 10 parts by weight of the SBS C solution prepared in Preparation Example 3 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Example 3

95 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 10 parts by weight of the SBS B solution prepared in Preparation Example 2 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Example 4

90 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 15 parts by weight of the SBS C solution prepared in Preparation Example 3 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Comparative Example 1

100 parts by weight of the SBS A solution (based on solid content) prepared in Preparation Example 1 was stripped, agglomerated, and dried to prepare a block copolymer composition pellet.

Comparative Example 2

95 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 5 parts by weight of the SBS D solution prepared in Preparation Example 4 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Comparative Example 3

90 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 10 parts by weight of the SBS E solution prepared in Preparation Example 5 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Comparative Example 4

90 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 10 parts by weight of the SBS F solution prepared in Preparation Example 6 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Comparative Example 5

80 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 20 parts by weight of the SBS B solution prepared in Preparation Example 2 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Comparative Example 6

70 parts by weight of the SBS A solution prepared in Preparation Example 1 (based on solid content) and 30 parts by weight of the SBS C solution prepared in Preparation Example 3 (based on solid content) were mixed for 10 hours, and the mixed solution was stripped, agglomerated, and dried. Thus, a block copolymer composition pellet was prepared.

Experimental example

Experimental Example 1

The content of the styrene block (SM) of each of the block copolymers prepared in Preparation Examples 1 to 6 and the content of vinyl group (Vinyl) in the conjugated diene block were measured through a 500 MHz NMR measuring device of Varian, and the following Table 1 Shown in.

division Manufacturing example One 2 3 4 5 6 SM content (weight%) 30 40 37 40 37 60 Vinyl content (weight%) 15 33 33 15 33 33

Experimental Example 2

In order to compare the solubility and physical properties of each of the block copolymer compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 as an asphalt modifier, 500 g of asphalt (SK AP-5) at 180° C. Each block copolymer composition prepared in Examples 1 to 4 and Comparative Examples 1 to 6 was calculated as 4.8% by weight and added, followed by mixing in a high shear stirrer (HSM, High Shear Mixer) at 2,500 rpm for 30 minutes. , 0.1 parts by weight of sulfur powder was added to 100 parts by weight of asphalt, and stirred at 300 rpm for 3 hours in a low shear stirrer (LSM, Low Shear Mixer), and the softening point, low temperature elongation, phase separation temperature and viscosity were measured in Table 2 below. Indicated.

* Softening Point (℃): According to ASTM D36, the asphalt composition specimen begins to soften when water or glycerin is heated at 5°C per minute, so that a bead with a diameter of 9.525 mm and a weight of 3.5 g placed on the specimen is 1 The temperature when sagging by an inch was measured.

* Low temperature elongation (mm, at 5°C): The length of the asphalt composition specimen was measured until immediately before the specimen was cut when the specimen was pulled in both directions in a thermostat maintained at 5°C according to ASTM D113. .

* Phase separation temperature (ΔT): 50 g of the asphalt composition prepared for each hour (1 hour, 2 hours, 3 hours) during low shear stirring was improved in an aluminum tube, and aged in an oven at 180° C. for 72 hours Then, it was divided into three and the softening points of the upper and lower parts were measured in the same manner as described above. In this case, it means that the solubility increases as the value of the phase separation temperature decreases.

* Viscosity (cps): When preparing the asphalt composition, after 3 hours of low shear stirring, the viscosity at each temperature of 135° C., 160° C. and 180° C. was measured using a Brookfield viscometer.

division Example Comparative example One 2 3 4 One 2 3 4 5 6 Softening point (℃) 88 87 88 87 85 84 88 82 73 69 Low temperature elongation at 5℃ (mm) 297 302 300 323 294 309 272 322 325 317 Phase separation temperature (△T, ℃) 1H 19.0 17.2 15.3 10.5 22.9 21.5 35.8 12.5 8.2 6.4 2H 4.5 3.1 3.0 1.5 11.0 12.5 17.0 2.1 3.1 0.3 3H 2.2 0.6 0.8 0.7 3.1 4.0 6.3 0.7 0.3 0.5 Viscosity
(cps) 135 ℃ 2,225 2,125 2,130 2,103 2,295 2,290 2,250 2,245 2,145 2,030 160 ℃ 765 735 725 712 780 790 785 730 720 701 180 ℃ 378 362 354 350 395 405 425 351 345 330

As shown in Table 2, a block copolymer composition obtained by mixing block copolymers satisfying the styrene block content and the vinyl group content of each of the first block copolymer and the second block copolymer defined in the present invention is an asphalt modifier. In the case of Examples 1 to 4 used as, compared to Comparative Example 1 using a single block copolymer, low-temperature elongation, phase separation temperature, and high-temperature viscosity were all improved, and in particular, it was confirmed that the softening point was significantly improved.

On the other hand, even if the content of the styrene block limited in the second block copolymer according to the present invention is satisfied, in the case of Comparative Example 2 including a block copolymer that does not satisfy the content of the vinyl group at the same time, it is confirmed that the softening point is rather lowered. In the case of Comparative Example 3, the softening point was improved, but it was confirmed that the low-temperature elongation, the phase separation temperature, and the high-temperature viscosity were very poor.

In addition, even if the content of the vinyl group limited in the second block copolymer according to the present invention is satisfied, in the case of Comparative Example 4 including a block copolymer that does not simultaneously satisfy the content of the styrene block, the softening point is rather lowered. I could confirm.

In addition, even if the content of the styrene block and the content of the vinyl group defined in the second block copolymer according to the present invention are satisfied, in the case of Comparative Examples 5 and 6 including an excessive amount of the second block copolymer, the softening point is rapidly decreased. I could confirm.

From the above results, the present inventors argue that when using the block copolymer according to the present invention as an asphalt modifier, while improving the solubility of the block copolymer composition and the low-temperature elongation and high-temperature viscosity of the asphalt composition to equal or higher levels, the softening point It was confirmed that this remarkably improved.

Claims (8)

More than 80% by weight to 99% by weight or less of the first block copolymer comprising a repeating unit block derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene-based monomer; And a second block copolymer comprising a repeating unit block derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer;
The content of the repeating unit block derived from the first aromatic vinyl monomer with respect to the total content of the first block copolymer is 20% by weight or more to less than 35% by weight, based on the total content of the repeating unit block derived from the first conjugated diene-based monomer The content of the vinyl group is 5% by weight or more and less than 25% by weight,
The content of the repeating unit block derived from the second aromatic vinyl monomer relative to the total content of the second block copolymer is 35% to 50% by weight, and a vinyl group based on the total content of the repeating unit block derived from the second conjugated diene-based monomer The content of Block copolymer composition of 25% to 50% by weight. The method of claim 1,
The content of the repeating unit block derived from the first aromatic vinyl monomer relative to the total content of the first block copolymer is 28% to 31% by weight, and the vinyl group based on the total content of the repeating unit block derived from the first conjugated diene-based monomer The content of the block copolymer composition is 13% by weight to 17% by weight. The method of claim 1,
Based on the total content of the second block copolymer, the content of the repeating unit block derived from the second aromatic vinyl monomer is 35% to 45% by weight, and the content of the repeating unit block derived from the second conjugated diene-based monomer is vinyl The content of the group is 25% by weight to 45% by weight of the block copolymer composition. The method of claim 1,
Based on the total content of the block copolymer composition, the content of the first block copolymer is 85% by weight to 97% by weight, and the content of the second block copolymer is 3% by weight to 15% by weight. In a hydrocarbon solvent, preparing a first block copolymer comprising a repeating unit derived from a first aromatic vinyl monomer and a repeating unit block derived from a first conjugated diene-based monomer (S10);
In a hydrocarbon solvent, preparing a second block copolymer comprising a repeating unit derived from a second aromatic vinyl monomer and a repeating unit block derived from a second conjugated diene-based monomer (S20); And
Mixing more than 80% by weight to 99% by weight of the first block copolymer prepared in step (S10) and 1% by weight to less than 20% by weight of the second block copolymer prepared in step (S20) Including (S30),
The content of the repeating unit block derived from the first aromatic vinyl monomer relative to the total content of the first block copolymer prepared in step (S10) is 20% by weight or more to less than 35% by weight, and derived from the first conjugated diene-based monomer The content of the vinyl group is from 5% by weight to less than 25% by weight,
The content of the repeating unit block derived from the second aromatic vinyl monomer with respect to the total content of the second block copolymer prepared in step (S20) is 35% by weight to 50% by weight, and the repeating unit derived from the second conjugated diene-based monomer A method for producing a block copolymer composition in which the content of the vinyl group is 25% by weight to 50% by weight based on the total block content. The method of claim 5,
The mixing of the step (S30) includes a first solution containing the first block copolymer prepared in the (S10) step and a second solution including the second block copolymer prepared in the (S20) step. A method for producing a block copolymer composition that is carried out by mixing. An asphalt composition comprising the block copolymer composition according to any one of claims 1 to 4 and asphalt. The method of claim 7,
The asphalt composition of the block copolymer composition is contained in an amount of 1% to 10% by weight based on the total content of the asphalt composition.