Asphalt composition containing linear diblock copolymer

专利摘要:
The present invention relates to an asphalt composition comprising a linear double block copolymer, in particular, an asphalt composition comprising a linear double block copolymer composed of vinyl aromatic hydrocarbon / conjugated diene has excellent dispersibility and excellent low temperature elongation and high softening point. In addition, when the linear double block copolymer is blended into the asphalt composition, the asphalt composition to which a small amount of the sulfur compound is added may further improve dispersibility to more easily improve low-temperature elongation and softening point.
公开号:KR20030046053A
申请号:KR1020010076370
申请日:2001-12-04
公开日:2003-06-12
发明作者:전문석；조재철；심규석；이춘화
申请人:주식회사 엘지화학；
IPC主号:

专利说明:

Asphalt composition comprising linear biblock copolymer {ASPHALT COMPOSITION CONTAINING LINEAR DIBLOCK COPOLYMER}
[1] The present invention relates to an asphalt composition comprising a linear double block copolymer, and more particularly to an asphalt composition having a significantly improved dispersibility, including a linear double block copolymer composed of vinyl aromatic hydrocarbon / conjugated diene.
[2] Asphalt, which serves to aggregate aggregate in road pavement, has a narrow operating temperature range of asphalt pavement due to problems such as cracking at low temperatures and plastic deformation at high temperatures. In addition, in recent years, the traffic volume has increased rapidly, and as the air temperature gradually rises due to global warming, the damage or deformation of the asphalt pavement has become more severe.
[3] For this reason, efforts have been made to improve and modify asphalt, and recently, studies on asphalt modifiers have been actively conducted as a way to maintain morphological stability at high and low temperatures of the asphalt / aggregate blend.
[4] Asphalt modifiers applied to date are mainly high molecular compounds, rubbery polymers such as olefin / acrylic monomer copolymers, vinyl aromatic hydrocarbons / conjugated diene random copolymers, and vinyl aromatic hydrocarbons / conjugated diene block copolymers, which are compatible with asphalt. Is known. Among them, the most effective high molecular compound is a vinyl aromatic hydrocarbon / conjugated diene block copolymer, and it has been found that the use of the copolymer has an effect of significantly widening the application temperature of asphalt. Since the amount of the copolymer is very small, the dispersibility of the copolymer is very important.
[5] Therefore, there is a further need for research on asphalt compositions comprising vinyl aromatic hydrocarbon / conjugated diene block copolymers that have dramatically improved dispersibility.
[6] In order to solve the above problems, an object of the present invention is to provide an asphalt composition having improved low temperature elongation and softening point, including a vinyl aromatic hydrocarbon / conjugated diene block copolymer having excellent dispersibility.
[7] In order to achieve the above object, the present invention
[8] a) asphalt; And
[9] b) linear diblock copolymers of vinyl aromatic hydrocarbon-conjugated dienes
[10] It provides an asphalt composition comprising a.
[11] In another aspect, the present invention provides an asphalt composition further comprising a sulfur compound in the composition.
[12] Hereinafter, the present invention will be described in detail.
[13] The inventors have found that the order-disorder transition temperature (T _ODT ) of a linear double block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene is a linear triple block copolymer composed of a vinyl aromatic hydrocarbon block, a conjugated diene block, a vinyl aromatic hydrocarbon block, and a radial type. Lower than the block copolymer. Therefore, when the linear double block copolymer is added to the asphalt, it was confirmed that the dispersibility is better at the same molecular weight than the linear triple block copolymer or the radial block copolymer, and thus the present invention was completed.
[14] The present invention provides an asphalt composition comprising a linear double block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene, and may further provide an asphalt composition further comprising a sulfur compound in the composition.
[15] The linear double block copolymer composed of the vinyl aromatic hydrocarbon and the conjugated diene is a vinyl aromatic hydrocarbon / conjugated diene copolymer having an average molecular weight in the range of 5,000 to 500,000, and the ratio of the vinyl aromatic hydrocarbon and the conjugated diene is 5:95 to 40:60. Is preferably. The linear double block copolymer also consists of a vinyl aromatic hydrocarbon, and a conjugated diene, and may comprise a vinyl aromatic hydrocarbon / conjugated diene copolymer block.
[16] The linear double block copolymer used in the present invention is a hydrocarbon solvent, a vinyl aromatic hydrocarbon, and a conjugated diene are added to a reactor with an organolithium compound, and a temperature of -50 to 150 ° C and a pressure at which the reactants can be maintained in the liquid phase. After the polymerization proceeds until the consumption rate of the monomer in the range of 0 to 10 bar or more than 99%, the polymerization is completed by removing the activity of the active polymer by adding water or alcohol.
[17] As the hydrocarbon solvent, n -pentane, n -hexane, n -heptane, isooctane, cyclohexane, toluene, benzene, xylene, various aromatic hydrocarbons, naphthalene hydrocarbons, etc. may be used, and preferably n -hexane, Cyclohexane, or a mixture thereof.
[18] In addition, a small amount of a polar solvent may be added to the hydrocarbon solvent, wherein the polar solvent serves to control the vinyl content and improve the polymerization rate during the conjugated diene polymerization. Examples of the polar solvent include tetrahydrofuran, ethyl ether, tetramethylethylenediamine, and the like, and particularly, tetrahydrofuran is preferably used.
[19] As the organolithium compound, an alkyl lithium compound may be used, and it is particularly preferable to use an alkyl lithium compound having an alkyl group having 3 to 10 carbon atoms. Examples thereof include methyl lithium, ethyl lithium, isopropyl lithium, n -butyl lithium, sec -butyl lithium, or tert -butyl lithium, and the like, preferably n -butyl lithium or sec -butyl lithium. will be.
[20] Examples of the vinyl aromatic hydrocarbons include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (ρ-metalphenyl) styrene, or One or more types of 1-vinyl-5-hexyl naphthalene etc. can be selected and used, Preferably styrene is used.
[21] Examples of the conjugated diene include 1,3-butadiene, 2,3-dimethel-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, or 2-phenyl-1,3-butadiene One or more types can be selected and used, Preferably 1, 3- butadiene is used.
[22] Mixing of the linear double block copolymer and asphalt as described above proceeds in the following manner.
[23] 500 g of asphalt are placed in a mixing vessel and the temperature is maintained at 150 ° C. and the stirring speed is 400 rpm, followed by the addition of a quantitative linear double block copolymer. Then slowly increase the stirring speed to 4,000 rpm and raise the temperature to 170 ℃ and stirred for 1 hour. In addition, in the case of adding the sulfur compound, the reaction proceeds by further stirring for 1 hour after adding the sulfur compound.
[24] The weight mixing ratio of the linear double block copolymer and asphalt is preferably in the range of 0.1: 99.9 to 20:80, more preferably in the range of 1:99 to 10:90.
[25] In addition, the sulfur compound which may be further included in the present invention is preferably a fine powder having a particle size of up to 100 mesh (mesh), wherein the molecular structure of sulfur is not important. In addition, the addition amount of the sulfur compound has a great influence on the physical properties of the asphalt / block copolymer, preferably the amount of the sulfur compound added is 0.001 ~ 0.2 pha (part / hundred asphalt).
[26] Asphalt composition according to the present invention, by using a linear double block copolymer composed of a vinyl aromatic hydrocarbon and conjugated diene having excellent dispersibility, excellent low-temperature elongation and softening point, as well as by further adding a small amount of sulfur compounds to the composition Low temperature elongation and softening point can be improved more easily.
[27] Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[28] EXAMPLE
[29] Example 1 Preparation of a Linear Double Block Copolymer
[30] A linear double block copolymer of styrene-butadiene having a styrene weight content of 15% was prepared in the following order.
[31] In a 20 L reactor substituted with nitrogen, 9,600 g of cyclohexane purified with a hydrocarbon solvent, 225 g of styrene with vinyl aromatic hydrocarbon, and 1,275 g of butadiene with conjugated diene were added thereto and stirred. When the temperature of the mixed solution reached 50 ° C., 0.4 g of n -butyllithium was added as an organolithium compound to polymerize styrene and butadiene.
[32] At this time, due to the polymerization characteristics, butadiene having high activity first participates in the polymerization, but the butadiene block is preferentially produced, and when butadiene is almost consumed, styrene participates in the polymerization to form a styrene block. Therefore, the activity of the produced active polymer is located at the end of the styrene block.
[33] As described above, after all monomers were consumed, 0.2 g of water was added to the reactor to remove the activity of the active polymer, thereby terminating the active copolymer. Next, 7.5 g of Irganox1076 (Ciba Specialty Chemicals Co.) and 15.0 g of TNPP (Weston Chemical Co.) were added to the polymerization solution to obtain a linear double block having a molecular weight of 200,000 g / mol and a styrene block content of 15% by weight. Copolymers were prepared.
[34] Comparative Example 1. Preparation of Triple Block Copolymer
[35] A linear triple block copolymer having a styrene weight content of 31% was prepared in the following order.
[36] Into a 20 L reactor substituted with nitrogen, 8,620 g of purified cyclohexane and 465 g of styrene were added and stirred. When the temperature of the mixed solution reached 60 ° C., 1.5 g of n -butyllithium was added to polymerize styrene, and then 1,035 g of butadiene was polymerized until butadiene was completely consumed. Subsequently, 1.725 g of dimethyl dichloride was added to the reactor for coupling reaction, and 0.2 g of water was added to the reactor to terminate the unreacted active copolymer. After that, 7.5 g of Irganox1076 (Ciba Specialty Chemicals Co.) and 15.0 g of TNPP (Weston Chemical Co.) were added to the polymerization solution, and a triple block having a molecular weight of 120,000 g / mol and a styrene block content of 31% by weight. Copolymers were prepared.
[37] Examples 2-6 and Comparative Examples 2-5. Asphalt composition manufacture
[38] Example 2
[39] 20.83 g of the linear double block copolymer prepared in Example 1 and 500 g of AP-5 asphalt having the physical properties shown in Table 1 were added to the mixing vessel, followed by stirring for 1 hour to prepare an asphalt composition.
[40] The physical properties of the asphalt are measured in the following manner.
[41] Penetration degree-After leaving for 3 hours at 25 ℃, it is measured according to ASTM 5.
[42] Softening point-Measured according to ASTM 36.
[43] Low Temperature Elongation—After standing at 5 ° C. for 3 hours, it is measured according to ASTM 113.
[44] Viscosity-measured according to ASTM 4402 using the Brookfield DV2 + Model
[45] (spindel number: 31).
[46] asphaltPenetration (dmm, 5 sec)Softening point (℃)Elongation (cm, 5 ℃)Viscosity (cps) 80 ℃100 ℃120 ℃ AP-564 to 6854.1 to 55.15>22,3004,0601,070
[47] Examples 3-6
[48] In the asphalt composition of Example 2, sulfur compounds (Sulfur Element, first-grade reagent, purity of 98% or more), respectively, 0.050 pha (part / hundred asphalt), 0.075 pha, 0.100 pha, 0.120 pha (0.25 by weight) g, 0.375 g, 0.5 g, 0.6 g) was added and stirred for 1 hour to prepare an asphalt composition.
[49] Comparative Example 2
[50] 20.83 g of the triple block copolymer prepared in Comparative Example 1 and 500 g of AP-5 asphalt having the physical properties shown in Table 1 were added to the mixing vessel, followed by stirring for 1 hour to prepare an asphalt composition.
[51] Comparative Examples 3 to 5
[52] To the asphalt composition of Comparative Example 2, the same sulfur compounds as in Examples 3 to 6 were added at 0.120 pha, 0.200 pha, and 0.250 pha, respectively (0.6 g, 1.0 g, and 1.25 g in terms of weight). The asphalt composition was prepared by stirring.
[53] The physical properties of the asphalt compositions prepared in Examples 2 to 6, and Comparative Examples 2 to 5 were measured by performing the same method as the physical properties of the asphalt of Example 2, the results are shown in Table 2 below.
[54] Asphalt compositionSulfur addition amount (pha)Penetration (dmm, 5 sec)Softening point (℃)Elongation (cm, 5 ℃)Viscosity (cps) 100 ℃120 ℃135 ℃ Example 205763.95.0>19,7004,9002,170 Example 30.0504570.631.529,9006,3202,540 Example 40.0754469.748.830,9006,7202,590 Example 50.1004676.060.037,7008,4003,120 Example 60.1205287.158.8284,00056,00020,000 Comparative Example 204572.535.518,2003,8401,520 Comparative Example 30.1205174.042.028,0005,3002,110 Comparative Example 40.2004978.440.338,4006,9302,550 Comparative Example 50.2504878.037.049,0008,0802,800
[55] As shown in Table 2, the asphalt of Examples 2 to 6 comprising the linear double block copolymer of the present invention was found to be superior to the asphalt of Comparative Examples 2 to 5 including the conventional triple block copolymer. . In addition, in Examples 3 to 6 in which the sulfur compound was added to the asphalt composition, physical properties and low-temperature elongation were significantly improved than those of the asphalt in Example 2 without the sulfur compound added.
[56] According to the present invention, it is possible to provide an asphalt composition having excellent low temperature elongation and an improved softening point, including a linear double block copolymer composed of a vinyl aromatic hydrocarbon having excellent dispersibility and a conjugated diene, and a small amount of sulfur compound in the composition. By further adding, the low-temperature elongation and softening point can be more easily improved.

权利要求:
Claims (8)
[1" claim-type="Currently amended] a) asphalt; And
b) linear diblock copolymers of vinyl aromatic hydrocarbon-conjugated dienes
Asphalt composition comprising a.
[2" claim-type="Currently amended] The method of claim 1,
Asphalt composition further comprising a sulfur compound in the composition.
[3" claim-type="Currently amended] The method of claim 1,
Asphalt composition whose weight ratio of the said vinyl aromatic hydrocarbon and conjugated diene is 5: 95-40: 60, and an average molecular weight is 5,000-500,000.
[4" claim-type="Currently amended] The method of claim 1,
The vinyl aromatic hydrocarbon is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (ρ-metalphenyl) styrene, and 1 Asphalt composition selected from the group which consists of -vinyl-5-hexyl naphthalene.
[5" claim-type="Currently amended] The method of claim 1,
The conjugated diene to 1,3-butadiene, 2,3-dimethel-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene Asphalt composition selected from the group which consists of 1 or more types.
[6" claim-type="Currently amended] The method of claim 1,
Wherein said linear double block copolymer is vinyl aromatic hydrocarbon is styrene and conjugated diene is butadiene.
[7" claim-type="Currently amended] The method of claim 1,
An asphalt composition in which the weight mixing ratio of the linear double block copolymer and asphalt is in the range of 0.1: 99.9 to 20:80.
[8" claim-type="Currently amended] The method of claim 2,
Asphalt composition having an addition amount of the sulfur compound 0.001-0.2 pha (part / hundred asphalt).

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同族专利:

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公开号 | 公开日

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KR100478126B1|2005-03-21|

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AU2002365855A1|2003-06-17|

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US20060229390A1|2006-10-12|

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JP2005513177A|2005-05-12|

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-12-04|Application filed by 주식회사 엘지화학

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2001-12-04|Priority to KR10-2001-0076370A

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2003-06-12|Publication of KR20030046053A

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2005-03-21|Application granted

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2005-03-21|Publication of KR100478126B1

优先权:

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申请号 | 申请日 | 专利标题

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KR10-2001-0076370A|KR100478126B1|2001-12-04|2001-12-04|Asphalt composition containing linear diblock copolymer|