KR101453127B1 - Modified asphalt composition and method for preparing modified asphalt - Google Patents
Modified asphalt composition and method for preparing modified asphalt Download PDFInfo
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- KR101453127B1 KR101453127B1 KR1020100093118A KR20100093118A KR101453127B1 KR 101453127 B1 KR101453127 B1 KR 101453127B1 KR 1020100093118 A KR1020100093118 A KR 1020100093118A KR 20100093118 A KR20100093118 A KR 20100093118A KR 101453127 B1 KR101453127 B1 KR 101453127B1
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Abstract
According to the asphalt modifier and the modified asphalt composition containing the sulfur and the vinyl aromatic hydrocarbon-conjugated diene block copolymer according to the present invention, the composition of the asphalt and the vinyl aromatic hydrocarbon-conjugated diene block copolymer and the sulfur in an amount of 10% Can be prevented and the asphalt composition excellent in softening point, low temperature elongation and elastic recovery rate can be provided.
Description
The present invention relates to a modified asphalt composition and a method for producing the modified asphalt using the same. More particularly, the present invention relates to a modified asphalt composition comprising asphalt and a mixture of two or more vinyl aromatic hydrocarbon-conjugated diene block copolymers asphalt modifier, The present invention relates to a modified asphalt composition containing a large amount of sulfur to prevent gel formation and improved physical properties of asphalt, and a process for producing modified asphalt using the modified asphalt composition.
Asphalt is used as a material for heated asphalt mixture, mainly used for road pavement, and acts as a binder to bind aggregates and aggregates well. General asphalt has very limited temperature range for asphalt pavement due to plastic deformation at high temperature and cracking at low temperature. Researches on asphalt modifiers for improving these problems have been actively conducted. It is known that the use of a polymeric compound, especially a vinyl aromatic hydrocarbon-conjugated diene block copolymer such as styrene-butadiene-styrene, as an asphalt modifier is most effective for improving high-temperature and low-temperature properties.
However, when the vinyl aromatic hydrocarbon - conjugated diene block copolymer is added to asphalt, the modified asphalt is separated into a heterogeneous phase because the affinity between the asphalt and the copolymer is small. Since the amount of the vinyl aromatic hydrocarbon-conjugated diene block copolymer to be added to the asphalt is very small, dispersion of the copolymer is very important. To solve this problem, a small amount of less than 5% of sulfur is added to the modified asphalt so that the asphalt and the copolymer Efforts have been made to increase the affinity of the compounds and are used as stabilizers for phase separation. However, when a large amount of sulfur of 10 wt% or more is used in the modified asphalt, a gel is formed and the viscosity thereof increases sharply, making it difficult to use as a binder. In the case of addition of a large amount of sulfur to general asphalt, the sulfur is inexpensive as compared with asphalt, so that a large amount of sulfur is added in terms of cost reduction, but the physical properties of the asphalt are lower than those of the modified asphalt.
Therefore, research has been conducted on an asphalt composition which improves physical properties without forming a gel even when a large amount of sulfur is added to the modified asphalt, and related arts are as follows.
U.S. Patent No. 4,412,019 discloses a modified asphalt composition prepared by adding 0-20% sulfur to the weight of asphalt in a butadiene-styrene block copolymer subjected to hydrogenation treatment to prevent gel formation.
U.S. Patent No. 5,756,566 discloses a modified asphalt composition prepared using 0.1 to 5% of an anti-gel agent based on the weight of an asphalt for the production of a gel-free asphalt-polymer compound.
Although the above-mentioned research has been conducted, a modified asphalt composition that significantly improves gel prevention when a large amount of sulfur is added to the modified asphalt is further required.
An object of the present invention is to provide a modified asphalt composition which can prevent generation of gel of modified asphalt while containing a large amount of sulfur in modified asphalt, and a process for producing modified asphalt using the modified asphalt composition.
The present invention also provides a modified asphalt composition capable of improving the physical properties of asphalt such as softening point, viscosity, low temperature elongation and elastic recovery rate, and a method for producing the modified asphalt using the same.
The above and other objects of the present invention can be achieved by the present invention described below.
In order to achieve the above object, the present invention uses two or more vinyl aromatic hydrocarbon-conjugated diene block copolymers as a modifier for modified asphalt.
The present invention provides an asphalt modifier and a modified asphalt composition comprising the same, wherein the modified asphalt modifier comprises a mixture of two or more vinyl aromatic hydrocarbon-conjugated diene block copolymers having different conjugated diene structures.
According to the present invention, when a modified asphalt composition is prepared by mixing two vinyl aromatic hydrocarbon-conjugated diene block copolymers, such as a mixture of a styrene-butadiene-styrene block copolymer and a styrene-isoprene-styrene block copolymer, with an asphalt Gel formation is prevented even when a large amount of sulfur is added, and an asphalt composition excellent in softening point, viscosity, low temperature elongation and elastic recovery rate can be provided.
Generally, when a large amount of sulfur is added to an aromatic hydrocarbon-conjugated diene block copolymer composition, crosslinking is caused by sulfur and a gel is formed. However, the vinyl aromatic hydrocarbon-conjugated diene block copolymer containing a structure such as an isoprene polymer has a delayed gel formation when a small amount of sulfur is added or under a certain temperature and concentration condition. Based on these characteristics, a block copolymer composition in which gel formation is prevented even when a large amount of sulfur is added is confirmed, and the present invention has been completed.
The present invention provides an asphalt modifier comprising a mixture of two or more vinyl aromatic hydrocarbon-conjugated diene block copolymers having different conjugated diene structures.
The vinyl aromatic hydrocarbon-conjugated diene block copolymer is a vinyl aromatic hydrocarbon-conjugated diene block copolymer having a vinyl aromatic hydrocarbon content of 5 to 50 parts by weight based on 100 parts by weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer.
The vinyl aromatic hydrocarbon-conjugated diene block copolymer is a vinyl aromatic hydrocarbon-conjugated diene block copolymer having a number average molecular weight of 5,000 to 1,000,000 g / mol.
The vinyl aromatic hydrocarbon may be selected from the group consisting of styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- Hexynaphthalene, and mixtures thereof, and the conjugated diene is at least one member selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, , 3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and mixtures thereof.
More preferably, the vinyl aromatic hydrocarbon-conjugated diene block copolymer may be a vinyl aromatic hydrocarbon-conjugated diene block copolymer wherein the vinyl aromatic hydrocarbon is polymerized with styrene or methylstyrene monomer, and the conjugated diene is polymerized with butadiene or isoprene monomer. More preferably, the vinyl aromatic hydrocarbon is styrene, and the conjugated diene is 1,3-butadiene or isoprene.
It is preferable that the mixture of the two or more vinyl aromatic hydrocarbon-conjugated diene block copolymers contains 50 wt% or more of the styrene-isoprene-styrene block copolymer in the total amount of the mixture. When the amount of the styrene-isoprene-styrene block copolymer is less than 50% by weight, a gel phenomenon occurs.
The present invention also relates to A) asphalt; B) said asphalt modifier comprising a mixture of two or more vinyl aromatic hydrocarbon-conjugated diene block copolymers having different conjugated diene structures; And C) sulfur. The present invention provides a modified asphalt composition comprising:
The content of the vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture is 1 to 10 parts by weight based on 100 parts by weight of the asphalt, and the sulfur content is 10 to 40 parts by weight based on 100 parts by weight of the asphalt. If the content of the vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture exceeds 10 parts by weight, dissolution time becomes long and it is not easy to completely dissolve. When the content of sulfur exceeds 40 parts by weight, generation of gel can not be controlled.
In the block copolymer used in the present invention, a vinyl aromatic hydrocarbon and a conjugated diene are added to a reactor having a hydrocarbon solvent and an organolithium compound as an initiator, the polymerization is continued until the consumption rate of the monomer is 99% or more, To produce a linear or branched block copolymer. Then, water or an alcohol is added to remove the activity of the polymer to terminate the polymerization. Add antioxidant and mix by stirring. The homogeneous block copolymer solution is stirred to remove the solvent by using steam to obtain a crumb-shaped block copolymer. Thereafter, dehydration and drying are performed to remove residual solvent and moisture.
The hydrocarbon solvent may be at least one selected from the group consisting of cyclopentane, cyclohexane, cycloheptane, benzene, naphthalene, toluene, xylene, pentane, hexane, heptane and octane.
The organic lithium compound may be at least one member selected from the group consisting of n-butyl lithium, sec-butyl lithium, methyl lithium, ethyl lithium, isopropyl lithium, cyclohexyl lithium, allyl lithium, vinyl lithium, phenyl lithium, But is not limited thereto.
The coupling agent may be at least one member selected from the group consisting of an aliphatic carboxylic acid, an aromatic carboxylic acid, an aliphatic chlorosilane, an aromatic chlorosilane, and a tetrachlorosilane.
The antioxidant may also be selected from the group consisting of n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tris (nonylphenyl) phosphite, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] or tris (2,4-di-t-butylphenyl) phosphite can be used.
The vinyl aromatic hydrocarbon-conjugated diene block copolymer thus prepared is blended with asphalt using a high-speed shear mixer and a low-speed shear mixer to obtain a modified asphalt.
The mixing process of asphalt is as follows.
The asphalt is placed in a 1 L vessel, the temperature is maintained at 180 ° C in a high speed shear mixer, the stirring speed is maintained at 2000 rpm, and a fixed amount of a block copolymer is introduced. Then, the stirring speed is gradually increased, and stirring is carried out for 1 hour while maintaining 3000 rpm. The asphalt and block copolymer composition is then cooled to 130 DEG C and then stirred in a low speed shear mixer. The temperature of the low speed shear mixer is maintained at 130 캜 and the stirring speed is 250 rpm, and a large amount of sulfur is added, followed by stirring for 30 minutes.
This modified asphalt is used to measure softening point, viscosity, low temperature elongation, and elastic recovery rate.
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 scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.
[Example]
Example One
Preparation of styrene-butadiene-styrene triblock copolymer
In a 10 L pressure-resistant reactor substituted with nitrogen, 4560 g of purified cyclohexane and 279 g of styrene were injected and maintained at 60 ° C. 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 butadiene polymerization, the coupling reaction was carried out by adding dichloromethylsilane. The polymerization reaction was terminated by adding 0.3 g of water to the polymerization solution, and n-octadecyl-3- (3,5-di- 16 g of t-butyl-4-hydroxyphenyl) propionate and tris (nonylphenyl) phosphite were added to obtain a linear styrene-butadiene-styrene block copolymer solution having a weight composition ratio of styrene and butadiene of 31:69.
The molecular weight of the prepared block copolymer was measured using high performance gel permeation chromatography (GPC). The detector was a Waters 2414 refractive index detector, the column temperature was 38 占 폚, and the solvent was THF. As a result, a styrene-butadiene-styrene triblock copolymer having a number average molecular weight of 120,000 g / mol and a styrene block content of 31% was obtained.
Preparation of styrene-isoprene-styrene block copolymer
4592 g of purified cyclohexane and 275 g of styrene were fed into a 10 L pressure-resistant reactor substituted with nitrogen and maintained at 60 ° C. N-butyllithium, an initiator, was added to a 32 g reactor to polymerize styrene. Five minutes after the polymerization temperature reached a maximum temperature, 609 g of isoprene was injected to produce an isoprene block at the end of the polymerized styrene block. After completion of the isoprene polymerization, 7.7 g of dichloromethylsilane was added to perform the coupling reaction. The polymerization reaction was terminated by adding 0.8 g of water to the polymerization solution, and the polymerization reaction was terminated. The n-octadecyl-3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate and tris (nonylphenyl) phosphite were added to obtain a linear styrene-isoprene-styrene block copolymer solution having a weight composition ratio of styrene and isoprene of 31:69 .
The molecular weight of the prepared block copolymer was measured by high performance gel chromatography (GPC). As a result, it was found that the block copolymer had a number average molecular weight of 148,000 g / mol and a styrene block content of 31% styrene-isoprene- To obtain a block copolymer solution.
Preparation of modified asphalt composition
The styrene-butadiene-styrene block copolymer solution and the styrene-isoprene-styrene triblock copolymer solution were put into water having a high temperature of 95 DEG C with TAMOL and calcium chloride as a dispersant to remove the solvent, After the copolymer was obtained, the solvent and moisture remaining after vacuum dehydration and oven drying were removed to prepare a triblock copolymer.
Styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer were prepared so that the sum of the styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer was 2.5 wt% Was 1: 1. The sulfur content was 20 parts by weight based on 100 parts by weight of the asphalt.
16 g of the mixed composition (1: 1) of the prepared styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer was blended with 500 g of asphalt for 1 hour in a high speed shear mixer, cooled to 130 캜, The mixture was blended with a large amount of sulfur in a blender for 30 minutes to obtain modified asphalt.
Example 2
The content of sulfur added to the mixed composition of asphalt, styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer (number average molecular weight: 106,000 g / mol) having a styrene content of 16% Except that the modified asphalt composition was made to be 20 parts by weight based on 100 parts by weight of the composition.
Comparative Example One
Example 1 was repeated except that the step of adding the block copolymer was omitted and only 20 parts by weight of sulfur was added to 100 parts by weight of the asphalt to prepare a modified asphalt composition.
Comparative Example 2
Example 1 was repeated except that 2.5 parts by weight of styrene-isoprene-styrene block copolymer and 20 parts by weight of sulfur were added to 100 parts by weight of asphalt to prepare a modified asphalt composition.
Comparative Example 3
The procedure of Example 1 was repeated except that the modified asphalt composition was prepared by mixing the styrene-butadiene-styrene block copolymer and the styrene-isoprene-styrene block copolymer in a ratio of 2: 1 in Example 1 Respectively.
Comparative Example 4
The procedure of Example 1 was repeated, except that the modified asphalt composition was prepared by mixing the styrene-butadiene-styrene block copolymer and the styrene-isoprene-styrene block copolymer in a ratio of 3: 2 in Example 1 Respectively.
Test Example
The softening point, viscosity, low temperature elongation and elastic recovery rate of the modified asphalt were measured. The asphalt used is an AP5 grade product with a softening point of 45.4 ° C, a 135 ° C viscosity of 452.5 cPs and an invasion of 71 mm.
Asphalt properties were measured by the following method.
(1) Softening point: Measured according to KS M 2250.
(2) Viscosity: Measured according to ASTM 4402 under the condition of spindle 31 using Brookfield DV1 + Model.
(3) Low temperature elongation: The specimen was left at 5 ° C and 10 ° C for 1 hour and measured according to ASTM 113.
(4) Elastic recovery rate: The specimen was left for 1 hour at 10 캜 and measured according to ASTM D 6083-97.
The results of the physical properties of the modified asphalt of Examples 1 to 2 and Comparative Examples 1 to 4 are shown in Table 1.
Asphalt composition
brimstone
Addition amount
(Parts by weight)
Block copolymer
(Parts by weight)
Softening point
(° C)
135 ℃
Viscosity
(cps)
Shout
Recovery rate
(%)
Low temperature elongation (cm)
* SBS: styrene-butadiene-styrene block copolymer
** SIS: styrene-isoprene-styrene block copolymer
As shown in Table 1, Examples 1 and 2 in which the styrene-butadiene-styrene block copolymer of the present invention and styrene-isoprene-styrene block copolymer were applied in a ratio of 1: 1 showed softening point, viscosity, low temperature elongation, Was superior to Comparative Example 1 in which a block copolymer was not applied and Comparative Example 2 in which a single block copolymer of styrene-isoprene-styrene was applied. Also, it can be confirmed that the gel was not formed in Example 1 in which the styrene-butadiene-styrene block copolymer and the styrene-isoprene-styrene block copolymer were applied in a ratio of 1: 1.
Claims (16)
B) an asphalt modifier comprising a mixture of two or more vinyl aromatic hydrocarbon-conjugated diene block copolymers having different conjugated diene structures; And
C) sulfur;
Wherein the sulfur content of the modified asphalt composition is 10 to 40 parts by weight based on 100 parts by weight of the asphalt.
Wherein the content of the vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture is 1 to 10 parts by weight based on 100 parts by weight of the asphalt.
The content of the vinyl aromatic hydrocarbon in the vinyl aromatic hydrocarbon-conjugated diene block copolymer is 5 to 50 parts by weight based on 100 parts by weight of the vinyl aromatic hydrocarbon-conjugated diene block copolymer and the number average molecular weight is 5,000 to 1,000,000 g / mol By weight of the modified asphalt composition.
The vinyl aromatic hydrocarbon may be selected from the group consisting of styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- Hexynaphthalene, and mixtures thereof, and the conjugated diene is at least one member selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, , 3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and mixtures thereof.
Wherein the vinyl aromatic hydrocarbon is styrene, and the conjugated diene is 1,3-butadiene or isoprene.
Wherein said vinyl aromatic hydrocarbon-conjugated diene block copolymer mixture comprises at least 50% by weight of styrene-isoprene-styrene block copolymer in the total mixture.
A second step of adding a mixture of two or more kinds of vinyl aromatic hydrocarbon-conjugated diene block copolymers having different conjugated diene structures to the above stirred product and stirring the mixture; And
And a third step of cooling the mixed mixture of asphalt and block copolymer and then adding sulfur while stirring.
Wherein the stirring in the first step is carried out at a stirring speed of 2000 rpm at 180 ° C.
Wherein the stirring in the second step is performed at a stirring speed of 3000 rpm.
Wherein the mixed asphalt and the block copolymer mixture are cooled to 130 캜 and then stirred under a stirring condition of 250 rpm in the third step.
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| KR102140124B1 (en) | 2016-11-22 | 2020-07-31 | 주식회사 엘지화학 | Modified asphalt composition |
| KR102133192B1 (en) * | 2018-08-09 | 2020-07-14 | 지에스칼텍스 주식회사 | Modified asphalt composition and method for preparing modified asphalt |
| CN113527604B (en) * | 2020-04-22 | 2024-06-11 | 中国石油化工股份有限公司 | Asphalt modifier and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5558703A (en) * | 1992-11-12 | 1996-09-24 | Fina Research, S.A. | Bituminous compositions |
| JPH10168323A (en) * | 1996-12-12 | 1998-06-23 | Sekiyu Sangyo Kasseika Center | Modified asphalt and its production |
| KR100492459B1 (en) | 2004-07-19 | 2005-06-02 | 주식회사 시티오브테크 | Material to improve quality of asphalt concrete, and the manufacturing method thereof |
| KR100680677B1 (en) | 2006-10-11 | 2007-02-08 | (주)에이알앤씨 | Recycling modified additive material for wast asphalt concrete and method for producing thereof |
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- 2010-09-27 KR KR1020100093118A patent/KR101453127B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5558703A (en) * | 1992-11-12 | 1996-09-24 | Fina Research, S.A. | Bituminous compositions |
| JPH10168323A (en) * | 1996-12-12 | 1998-06-23 | Sekiyu Sangyo Kasseika Center | Modified asphalt and its production |
| KR100492459B1 (en) | 2004-07-19 | 2005-06-02 | 주식회사 시티오브테크 | Material to improve quality of asphalt concrete, and the manufacturing method thereof |
| KR100680677B1 (en) | 2006-10-11 | 2007-02-08 | (주)에이알앤씨 | Recycling modified additive material for wast asphalt concrete and method for producing thereof |
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