KR101411159B1 - Triarm type vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving heat stability of asphalt, method of manufacturing the same, and asphalt composition comprising the same - Google Patents
Triarm type vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving heat stability of asphalt, method of manufacturing the same, and asphalt composition comprising the same Download PDFInfo
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Abstract
The present invention relates to a tri-branched-type vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving the thermal stability of asphalt, a process for producing the same, and an asphalt composition containing the same, wherein the tri-branched vinyl aromatic hydrocarbon- , A triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving the thermal stability of an asphalt containing an antioxidant and an enol ether compound as an ozone deterioration inhibitor. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an asphalt composition in which the thermal stability at a high temperature is remarkably improved by using the triplet branched vinyl aromatic-conjugated diene copolymer composition containing an ozone deterioration inhibitor.
Description
The present invention relates to a triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving the thermal stability of asphalt, and more particularly, to a composition for improving the thermal stability of asphalt by using an ozone deterioration inhibitor and a triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer , A triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition capable of improving thermal stability of asphalt, a process for producing the same, and an asphalt composition containing the same.
Unmodified asphalt is limited in its use due to plastic deformation at high temperatures and cracking at low temperatures. In order to solve such problems, various studies have been made to improve physical properties by adding various polymers.
Vinyl aromatic hydrocarbon-conjugated diene block copolymers such as styrene-butadiene-styrene block copolymers exhibit excellent effects at high temperature and low temperature properties, and thus they are most widely used in industrial fields such as road pavement and roof waterproofing as contained in asphalt.
In the case of road or waterproof asphalt compositions, flow resistance at high temperatures and flexural properties at low temperatures are major property evaluation factors. The roadside asphalt composition should be stored at a high temperature of 150 to 180 占 폚 for several hours or possibly several days due to waiting for transportation or paving work for pavement of roads. In this case, the styrene-butadiene- There arises a problem that the styrene copolymer is decomposed to lower the softening point of the asphalt composition.
U.S. Patent No. 4,485,201 discloses an antioxidant for imparting heat resistance to a blend mainly comprising a waste tire rubber powder and a styrene-butadiene-styrene block copolymer (linear or branched) as an asphalt, a hydrogenated rosin-based tackifier a tackifying agent, a plasticizer, or an asphalt composition to which a processing oil is added as a softening agent.
SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of conventional asphalt compositions. By using an ozone deterioration inhibitor and a triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer, it is possible to improve the thermal stability of asphalt Vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
Another object of the present invention is to provide a process for preparing the above-mentioned tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
It is still another object of the present invention to provide a modified asphalt composition comprising the above-mentioned tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
In order to achieve the above object, the present invention provides a tri-branched polyvinyl aromatic hydrocarbon for improving the thermal stability of an asphalt, which comprises an enol ether compound as an antioxidant and an ozone deterioration inhibitor, -Conjugated diene block copolymer composition.
In the present invention, the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition may further include a linear vinyl aromatic hydrocarbon-conjugated diene block copolymer.
In the present invention, the phenol ether compound is selected from the group consisting of vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2,3-dihydrofuran, furan, pyran, dibenzyl ether and 4- (benzyloxymethylene) Cyclohexene, and cyclohexene.
The content of the ozone deterioration inhibitor in the present invention is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer.
The content of the ozone deterioration inhibitor in the present invention is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the mixture of the tri-branched type vinyl aromatic-hydrocarbon-conjugated diene block copolymer and the linear vinyl aromatic-hydrocarbon-conjugated diene block copolymer.
In the present invention, the vinyl aromatic hydrocarbon monomer is selected from the group consisting of styrene, alphamethylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- -Vinyl-5-hexynaphthalene. ≪ / RTI >
In the present invention, the conjugated diene monomer may be 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3- Butadiene. ≪ / RTI >
In the present invention, the content of the vinyl aromatic hydrocarbon in the tri-branched-type vinyl aromatic-hydrocarbon-conjugated diene block copolymer is preferably 5 to 50% by weight based on the total weight of the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer.
In the present invention, the number average molecular weight of the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer is preferably 10,000 to 1,000,000 g / mol.
The present invention also provides a method for preparing a vinyl aromatic hydrocarbon block polymer, comprising the steps of: (a) forming a first mixed solution containing a living vinyl aromatic hydrocarbon block polymer by polymerizing a vinyl aromatic hydrocarbon monomer using an organolithium compound as a polymerization initiator in a hydrocarbon solvent; (b) Forming a second mixed solution comprising a living vinyl aromatic hydrocarbon-conjugated diene diblock copolymer by adding a monomer to a first mixed solution to form a conjugated diene block at the end of the vinyl aromatic hydrocarbon block polymer; (c) adding a coupling reagent to the second mixed solution and performing a coupling reaction, thereby forming a third mixed solution containing the triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer; (d) adding an enol ether compound as an antioxidant and an ozone deterioration inhibitor to a third mixed solution and stirring to form a fourth mixed solution; And (e) dehydrating and drying the fourth mixed solution to obtain a triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition comprising an antioxidant and an ozone deterioration inhibitor. There is provided a process for producing a branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
The third mixed solution of step (c) in the manufacturing method of the present invention may further comprise a linear vinyl aromatic hydrocarbon-conjugated diene block copolymer, and the triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer of step (e) The composition may further comprise a linear vinyl aromatic hydrocarbon-conjugated diene block copolymer.
In the present invention, the hydrocarbon solvent may be at least one selected from cyclopentane, cyclohexane, cycloheptane, benzene, naphthalene, toluene, xylene, pentane, hexane, heptane and octane.
In the present invention, the organolithium compound may be at least one member selected from n-butyllithium, sec-butyllithium, methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allylithium, vinyllithium, phenyllithium and benzyllithium .
The present invention also provides an asphalt composition comprising a tri-branched, vinyl aromatic hydrocarbon-conjugated diene block copolymer composition.
The asphalt composition of the present invention preferably comprises 1 to 20 parts by weight of a tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition based on 100 parts by weight of asphalt.
By using the antioxidant and the ozone deterioration inhibitor in the composition of the triplet branched vinyl aromatic-hydrocarbon-conjugated diene block copolymer according to the present invention, the ozone deterioration inhibitor, together with the antioxidant, It is possible to inhibit the cleavage of the double bond in the aromatic hydrocarbon-conjugated diene block copolymer. Further, by using the triplet branched vinyl aromatic-conjugated diene block copolymer in place of the existing linear vinyl aromatic-hydrocarbon conjugated diene block copolymer, it is possible to reduce the effect of the double bond cleavage by ozone and oxygen when stored at a high temperature for a long time . Thus, the thermal stability of the asphalt can be remarkably improved by minimizing the decrease of the softening point temperature compared with the conventional asphalt composition.
Also, in the production method of the present invention, an antioxidant and an ozone deterioration inhibitor are continuously added to a reactor in which a tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer is polymerized to obtain a tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition So that the composition components are uniformly mixed and the manufacturing process is simple.
Further, the triplet branched vinyl aromatic-conjugated diene block copolymer composition of the present invention is a solid form in which an antioxidant and an ozone deterioration inhibitor are preliminarily mixed and is easy to handle during kneading with asphalt, and the kneading process is simple, There is an advantage that an asphalt composition can be stably produced.
Further, the asphalt composition comprising the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition of the present invention exhibits excellent thermal stability.
Hereinafter, the present invention will be described in detail with reference to examples.
The triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving thermal stability of asphalt according to the present invention contains an enol ether compound as an antioxidant and an ozone deterioration inhibitor in a triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer do.
Tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer
The triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving the thermal stability of asphalt according to the present invention is characterized in that triple branched vinyl aromatic-hydrocarbon diene block copolymer . Here, the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition may further include a linear vinyl aromatic hydrocarbon-conjugated diene block copolymer.
The vinyl aromatic hydrocarbon-conjugated diene block copolymer is obtained by polymerizing a vinyl aromatic hydrocarbon monomer and a conjugated diene monomer.
Examples of the vinyl aromatic hydrocarbon monomer include styrene, alphamethylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- -5-hexynaphthalene may be used alone or in combination of two or more.
Examples of the conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, They may be used alone or in combination of two or more.
More preferably, styrene or methylstyrene can be used singly or in combination as the vinyl aromatic hydrocarbon monomer, and as the conjugated diene monomer, butadiene or isoprene can be used singly or in combination.
When the block copolymer is used, the content of each block may be varied and mixed. The content of the vinyl aromatic hydrocarbon in the tri-branched or linear vinyl aromatic-hydrocarbon-conjugated diene block copolymer is preferably 5 to 50% by weight based on the total weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer. When the content of the vinyl aromatic hydrocarbon is less than 5% by weight, the physical properties of the asphalt deteriorate due to the difficulty of the physical cross-linking of the vinyl aromatic hydrocarbon block. When the content exceeds 50% by weight, the solubility in the asphalt is poor and the low- .
The number average molecular weight of the tri-branched or linear vinyl aromatic hydrocarbon-conjugated diene block copolymer is preferably 10,000 to 1,000,000 g / mol. When the number average molecular weight is less than 10,000 g / mol, the number average molecular weight of the vinyl aromatic hydrocarbon block is too small, which deteriorates the physical properties at high temperature. When the number average molecular weight is more than 1,000,000 g / mol, the solubility in the asphalt is remarkably decreased.
Ozone deterioration inhibitor
In order to maintain the reduction of the softening point temperature to a minimum and to improve the thermal stability by suppressing the double bond cleavage in the triplet branched or linear vinyl aromatic-conjugated diene block copolymer by ozone at a high temperature for a long time, , The triplet branched vinyl aromatic-conjugated diene block copolymer composition according to the present invention includes an ozone deterioration inhibitor.
The reaction mechanism for ozone deterioration, in which the hydrocarbon double bond is cleaved (ozonolysis) by ozone deterioration, is as shown in Scheme 1.
[Reaction Scheme 1]
As shown in Reaction Scheme 1, a double bond is cleaved by ozone (O 3 ) to produce a carbonyl group. Particularly, the cleavage of the double bonds due to ozone occurs at high temperatures. The ozone concentration, the incidence rate, and the temperature are influential factors in deterioration by ozone. Such cleavage of the hydrocarbon double bond by ozone can be suppressed by using an ozone deterioration inhibitor. Instead of reacting with the double bond, ozone reacts with the ozone deterioration inhibitor to inhibit the cleavage of the double bond.
The triplet branched vinyl aromatic-conjugated diene block copolymer composition of the present invention can use an enol ether compound as an ozone deterioration inhibitor.
Examples of the enol ether compounds include vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2,3-dihydrofuran, furan, May be used alone or in combination of two or more.
The content of the ozone deterioration inhibitor is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the tri-branched type vinyl aromatic hydrocarbon-conjugated diene block copolymer. When the content of the ozone deterioration inhibitor is less than 0.01 part by weight based on 100 parts by weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer, the effect is insufficient and undesirable. When the content exceeds 10 parts by weight, the content of the vinyl aromatic hydrocarbon- The absolute amount is reduced and the physical properties of the modified asphalt are seriously deteriorated.
When the triplet branched vinyl aromatic-hydrocarbon conjugated diene block copolymer composition of the present invention further comprises a linear vinyl aromatic hydrocarbon-conjugated diene block copolymer, the content of the ozone deterioration inhibitor is preferably in the range of from 0.1 to 50 parts by weight based on the triplet branched vinyl aromatic hydrocarbon- Is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of a mixture of a block copolymer and a linear vinyl aromatic-hydrocarbon conjugated diene block copolymer. When the content of the ozone deterioration inhibitor is less than 0.01 part by weight based on 100 parts by weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture, the effect is insignificant and if it is more than 10 parts by weight, the vinyl aromatic hydrocarbon-conjugated diene block copolymer The absolute amount of the asphalt is reduced and the physical properties of the modified asphalt are seriously deteriorated.
Antioxidant
Examples of the antioxidant that can be used in the vinyl aromatic hydrocarbon-conjugated diene block copolymer composition of the present invention include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and specific examples include n-octadecyl-3- 3,5-di -t- butyl-4-hydroxyphenyl) propionate, 2,6-di -tert- butyl - p - cresol, 4,6-bis (dodecyl thiomethyl) - o - cresol, (Octylthiomethyl) -o -cresol, benzenepropionic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-C 7-9 branched alkyl ester, tris Butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) Octyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite and poly 4,4-isopropylidenediphenol-C12-15 alcohol phosphite may be used alone or in combination of two or more. ≪ RTI ID = 0.0 & Can be used without limitation.
The content of the antioxidant is preferably 0.1 to 3 parts by weight, more preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer. When the content of the antioxidant is less than 0.1 part by weight, the vinyl aromatic hydrocarbon-conjugated diene block copolymer is not effectively prevented from being oxidized, and when it exceeds 3 parts by weight, the absolute amount of the polymer product is decreased, And the antioxidant is added to the antioxidant more than necessary to increase the cost of the product, which is commercially undesirable.
When the triplet branched vinyl aromatic-hydrocarbon conjugated diene block copolymer composition of the present invention further comprises a linear vinyl aromatic hydrocarbon-conjugated diene block copolymer, the content of the antioxidant is preferably in the range of from 0.1 to 50 parts by weight based on the triplet branched vinyl aromatic hydrocarbon- It is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the mixture of the copolymer and the linear vinyl aromatic hydrocarbon-conjugated diene copolymer. When the content of the antioxidant is less than 0.1 part by weight based on 100 parts by weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture, it is not preferable because it does not effectively block the oxidation of the vinyl aromatic hydrocarbon-conjugated diene block copolymer, The absolute amount of the polymer product may be reduced to cause deterioration of the properties of the application field and commercialization of the antioxidant is not preferable due to the increase of the cost of the product.
Manufacturing method
The method for producing a tri-branched-type vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving thermal stability of asphalt according to the present invention comprises the steps of (a) polymerizing a vinyl aromatic hydrocarbon monomer using an organolithium compound as a polymerization initiator in a hydrocarbon solvent, (B) adding a conjugated diene monomer to the first mixed solution to form a conjugated diene block at the end of the vinyl aromatic hydrocarbon block polymer, thereby forming a living vinyl aromatic hydrocarbon-conjugated Forming a second mixed solution comprising a diene diblock copolymer; (c) adding a coupling reagent to the second mixed solution and performing a coupling reaction, thereby forming a third mixed solution containing the triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer; (d) adding an enol ether compound as an antioxidant and an ozone deterioration inhibitor to a third mixed solution and stirring to form a fourth mixed solution; And (e) dehydrating and drying the fourth mixed solution to obtain a tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition containing an antioxidant and an ozone deterioration inhibitor.
In the step (a), the polymerization reaction is preferably continued until the vinyl aromatic hydrocarbon monomer is consumed by 99% or more, and in the step (b), the polymerization reaction is preferably continued until the conjugated diene monomer is consumed at least 99% Do.
In the step (c), a trifunctional vinyl aromatic hydrocarbon-conjugated diene block copolymer or a trifunctional vinyl aromatic hydrocarbon-conjugated diene block copolymer is obtained by adding a 3-functional group coupling agent or a 2-functional group and 3-functional group coupling agent to the second mixed solution, A linear vinyl aromatic hydrocarbon-conjugated diene and a tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer are prepared, and then water or an alcohol is added to the reactor to remove the activity of the polymer.
As the bifunctional group coupling reaction agent, dichloromethylsilane, diethyltrimethylsilane, dichloromethyldiphenylsilane and the like can be used. As the trifunctional group coupling reaction agent, methyl trichlorosilane, ethyl trichloride, phenylsilane trichloride and the like can be used .
In step (d), the antioxidant and the ozone deterioration inhibitor are added to the third mixed solution of step (c), and the mixture is homogeneously mixed.
In the step (e), the solvent is removed from the homogenized fourth mixed solution using high-temperature water or steam to obtain a crumb-shaped block copolymer. Thereafter, the remaining solvent and moisture are removed through dehydration and drying, And an ozone deterioration inhibitor are uniformly obtained.
As the hydrocarbon solvent, cyclopentane, cyclohexane, cycloheptane, benzene, naphthalene, toluene, xylene, pentane, hexane, heptane and octane may be used singly or in combination of two or more.
As the organic lithium compound, n-butyl lithium, sec-butyl lithium, methyl lithium, ethyl lithium, isopropyl lithium, cyclohexyl lithium, allyl lithium, vinyl lithium, phenyl lithium and benzyl lithium have.
As the coupling reaction agent, an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic chloride silane, an aromatic chloride silane, and a tetrachlorosilane can be used singly or in combination of two or more kinds.
The modified asphalt composition
Asphalt is obtained as a residue when refining crude oil, mainly composed of hydrogen and carbon, and consists of a hydrocarbon compound with a small amount of nitrogen, sulfur or oxygen.
Examples of asphalt include straight asphalt, cutback asphalt, goose asphalt, blown asphalt, emulsified asphalt or sebum (PG) grade asphalt.
Straight asphalt is the final residue obtained by distillation of the crude oil from the atmospheric distillation column (CDU) and then distillation under reduced pressure of the residual atmospheric residue (AR). Since it contains a large amount of non-decomposed bituminous material, it can be used as a raw material for various petroleum-based asphalt have. Commercialized straight asphalt is AP-3, AP-5, etc. supplied by SK Energy or GS Caltex.
The modified asphalt composition of the present invention comprises a tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving the thermal stability of the asphalt.
The content of the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition in the asphalt composition is 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the asphalt. When the content of the tri-branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition is less than 1 part by weight based on 100 parts by weight of the asphalt, the asphalt modifying effect is not exhibited. When the content is more than 20 parts by weight, the vinyl aromatic hydrocarbon- It is difficult to uniformly dissolve the composition in the asphalt so that the processability of the modified asphalt is poor and the production cost of the vinyl aromatic hydrocarbon-conjugated diene block copolymer composition is higher than that of the asphalt, thereby reducing the economical efficiency of the modified asphalt composition.
The modified asphalt composition of the present invention can be used as an ozone deterioration inhibitor, which is an antioxidant, an ozone deterioration inhibitor as a thermal stability improver, at a high speed It can be obtained by mixing with asphalt with a shear mixer.
The mixing procedure of the modified asphalt composition is as follows. The asphalt was placed in a 1 L vessel and maintained at a temperature of 150 ° C. for 1 hour to 1 hour and 30 minutes to obtain a molten state. The vinyl aromatic hydrocarbon-conjugated diene block copolymer composition was gradually added into the asphalt . The stirrer speed was maintained at 2,500 rpm and stirred for 2 hours while adjusting to 170 캜. The modified asphalt composition thus prepared is stored in an oven at 180 ° C. for a certain period of time, and then the softening point at high temperature is measured.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. , And it is natural that such variations and modifications fall within the scope of the appended claims.
Example 1
4,560 g of purified cyclohexane and 279 g of styrene were fed into a 10 L pressure-resistant reactor substituted with nitrogen and maintained at 60 ° C. Next, n-butyllithium, an initiator, was added to the reactor to polymerize the styrene. Five minutes after the polymerization temperature reached the maximum temperature, 621 g of butadiene was injected to produce a butadiene block at the end of the polymerized styrene block. After completion of polymerization of the butadiene, 0.82 g of methylcyclohexylmethylsilane as a coupling agent was added to conduct the coupling reaction. Then, 0.3 g of water was added to the polymerization solution to terminate the polymerization reaction. Next, 3.6 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as an antioxidant and 8.1 g of trisnonylphenyl phosphite were added, 0.9 g of 4- (benzyloxymethylene) cyclohexene, which is a deterioration inhibitor, was added to obtain a triplet branched and linear styrene-butadiene-styrene block copolymer composition having a weight composition ratio of styrene to butadiene of 31:69. The weight ratio of the tri-branched block copolymer to the linear block copolymer was 85:15.
The number average molecular weight of the triplet branched and linear styrene-butadiene-styrene block copolymers prepared above was measured using high performance gel permeation chromatography (GPC). At this time, a Waters 2414 refractive index detector was used as a detector, a column temperature was 38 ° C, and THF was used as a solvent. As a result of the measurement, the styrene-butadiene-styrene block copolymer had a number average molecular weight of 165,000 g / mol and a coupling efficiency of 85%.
The prepared styrene-butadiene-styrene block copolymer composition solution was poured into water at a high temperature of 95 占 폚 with a dispersant to remove the solvent to obtain a crumb-shaped tri-branched styrene-butadiene-styrene block copolymer composition. Thereafter, the remaining solvent and moisture were removed through vacuum dehydration and oven drying to obtain a tri-branched styrene-butadiene-styrene block copolymer composition containing an antioxidant and an ozone deterioration inhibitor. In order to minimize the effect of particle size on the thus obtained crumb, only 14 mesh residues passing through 2 mesh sieves were used in the experiment.
In accordance with the above-mentioned method, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, which is an antioxidant, is added to 100 parts by weight of a tri-branched styrene-butadiene- A styrene-butadiene-styrene block copolymer composition was prepared so that 0.4 part by weight of trisnonylphenyl phosphite, 0.9 part by weight of trisnonylphenyl phosphite and 0.1 part by weight of 4- (benzyloxymethylene) cyclohexene as an antioxidant ozone deterioration inhibitor.
32 g of the tri-branched styrene-butadiene-styrene block copolymer composition containing the antioxidant prepared above and 600 g of asphalt were blended in a high speed shear mixer for 2 hours to obtain a modified asphalt composition. The softening point was measured after storage for 10, 24 hours. As the asphalt, an AP 5 grade product having a softening point of 47 ° C and a viscosity of 180 cPs at 180 ° C was used.
The softening point was measured according to KS M 2250.
Example 2
Except that 0.5 parts by weight of 4- (benzyloxymethylene) cyclohexene as an antioxidant ozone deterioration inhibitor based on 100 parts by weight of a styrene-butadiene-styrene block copolymer mixture was used.
Example 3
Except that 1 part by weight of 4- (benzyloxymethylene) cyclohexene as an antioxidant ozone deterioration inhibitor based on 100 parts by weight of a styrene-butadiene-styrene block copolymer mixture was used.
Example 4
Except that 3 parts by weight of 4- (benzyloxymethylene) cyclohexene which is an antioxidant ozone deterioration inhibitor based on 100 parts by weight of a styrene-butadiene-styrene block copolymer mixture was used.
Example 5
In order to produce 55 parts by weight of a tri-branched styrene-butadiene-styrene block copolymer and 45 parts by weight of a linear styrene-butadiene-styrene block copolymer, 1.06 g of a coupling agent trichloromethylsilane was added to perform a coupling reaction, Except that 0.5 parts by weight of 4- (benzyloxymethylene) cyclohexene as an antioxidant ozone deterioration inhibitor based on 100 parts by weight of a styrene-butadiene-styrene block copolymer mixture was used. At this time, the weight ratio of the tri-branched block copolymer to the linear block copolymer was 55:45.
Comparative Example 1
The same as Example 1 except that no ozone deterioration inhibitor was used.
Comparative Example 2
To obtain a linear styrene-butadiene-styrene block copolymer, 1.04 g of a coupling agent dichlorosilane was added to perform a coupling reaction. 100 parts by weight of the prepared linear styrene-butadiene-styrene block copolymer (tri-branched block copolymer (Benzyloxymethylene) cyclohexene, which is an antioxidant deterioration inhibitor for an ozone-based ozone, based on 100 parts by weight of the antioxidant.
Comparative Example 3
Styrene-butadiene-styrene block copolymer mixture was used in an amount of 0.5 parts by weight, based on 100 parts by weight of the mixture, of paraphenylenediamine-based compound, 0.5 part by weight, as an ozone deterioration inhibitor.
Test Example
The results of the physical properties of the modified asphalt of Examples and Comparative Examples are shown in Table 1.
Table 1 shows the composition of the tri-branched styrene-butadiene-styrene block copolymer composition of Examples and Comparative Examples, and the softening point of the asphalt composition containing the block copolymer composition, wherein the asphalt composition is based on 100 parts by weight of asphalt And 5 parts by weight of a styrene-butadiene-styrene block copolymer composition.
As shown in Table 1, the addition amount of 4- (benzyloxymethylene) cyclohexene, which is one of the ozone antioxidants, to the mixture of the tri-branched styrene-butadiene-styrene block copolymer and the linear styrene-butadiene- To 3 parts by weight, it can be seen that the time during which the initial softening point of the asphalt composition is maintained at 90% or more during the oven storage is increased up to 24 hours as compared with the case where it is not added.
This is due to the fact that trifunctional styrene-butadiene with 4- (benzyloxymethylene) cyclohexene added to the mixture of tri- and branched-styrene-butadiene-styrene block copolymers without 4- (benzyloxymethylene) cyclohexene- - styrene block copolymer does not decompose all at once and pyrolysis takes place in only one of the three types, resulting in delayed pyrolysis compared with the linear single block copolymer. In addition, in the block copolymers mixed with 4- (benzyloxymethylene) cyclohexene It is understood that the effect of delaying the thermal decomposition is added to increase the thermal stability.
When 4- (benzyloxymethylene) cyclohexene is used in the case where the content of the tri-branched block copolymer is 55% by weight based on the total weight of the block copolymer mixture (Example 5) It can be said that the above reason is that the holding time of the softening point of 90% is increased up to 24 hours compared with Comparative Example 1 containing 85% by weight of the branched block copolymer.
On the other hand, in the case where only a linear styrene-butadiene-styrene block copolymer was used (Comparative Example 2) without using a tri-branched styrene-butadiene-styrene block copolymer at all, and a similar ozone deterioration inhibitor, 6-paraphenylenediamine (Comparative Example 3) had substantially the same result as that in the case of not using it, and it was found that there was no effect.
Claims (17)
Antioxidants; And
An ozone deterioration preventing agent containing an enol ether compound,
A triple branched type vinyl aromatic hydrocarbon - conjugated diene block copolymer composition for improving thermal stability of asphalt.
(b) adding a conjugated diene monomer to the first mixed solution to form a conjugated diene block at the end of the vinyl aromatic hydrocarbon block polymer, thereby forming a second mixed solution containing the living vinyl aromatic hydrocarbon-conjugated diene diblock copolymer;
(c) adding at least one coupling agent selected from the group consisting of dichloromethylsilane, dichloromethylsilane, dichloromethylsilane, methylchlorosilane, trichlorosilane, and trichlorosilane to the second mixed solution, Coupling reaction to form a third mixed solution containing a mixture of a triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer and a linear vinyl aromatic hydrocarbon-conjugated diene block copolymer, wherein, based on 100 parts by weight of the mixture, 55 to 85 parts by weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer and 15 to 45 parts by weight of the linear vinyl aromatic-hydrocarbon-conjugated diene block copolymer;
(d) adding an enol ether compound as an antioxidant and an ozone deterioration inhibitor to a third mixed solution and stirring to form a fourth mixed solution; And
(e) dehydrating and drying the fourth mixed solution to obtain a mixed composition of the triplet branched vinyl aromatic-hydrocarbon conjugated diene block copolymer and the linear vinyl aromatic hydrocarbon-conjugated diene block copolymer containing an antioxidant and an ozone deterioration inhibitor ≪ / RTI >
A method for producing a triplet branched vinyl aromatic hydrocarbon-conjugated diene block copolymer composition for improving thermal stability of asphalt.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102275171B1 (en) * | 2020-12-07 | 2021-07-08 | 중앙방수기업 주식회사 | Self-adhesion type asphalt waterproofing sheet manufacturing method and complex waterproof method using thereof |
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| KR102244902B1 (en) * | 2016-12-28 | 2021-04-26 | 주식회사 엘지화학 | Asphalt modifier and modified asphalt composition comprising the same |
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| US4878950A (en) | 1988-04-29 | 1989-11-07 | Exxon Chemical Patents Inc. | Bitumen composition |
| US20040054090A1 (en) * | 2002-07-11 | 2004-03-18 | Kraton Polymers U.S. Llc | Coupled styrenic block copolymers and process for preparing same |
| KR20100017141A (en) * | 2007-04-20 | 2010-02-16 | 헤리티지 리서치 그룹 | Polymer-modified asphalt compositions |
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Patent Citations (3)
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| US4878950A (en) | 1988-04-29 | 1989-11-07 | Exxon Chemical Patents Inc. | Bitumen composition |
| US20040054090A1 (en) * | 2002-07-11 | 2004-03-18 | Kraton Polymers U.S. Llc | Coupled styrenic block copolymers and process for preparing same |
| KR20100017141A (en) * | 2007-04-20 | 2010-02-16 | 헤리티지 리서치 그룹 | Polymer-modified asphalt compositions |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102275171B1 (en) * | 2020-12-07 | 2021-07-08 | 중앙방수기업 주식회사 | Self-adhesion type asphalt waterproofing sheet manufacturing method and complex waterproof method using thereof |
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