WO2020119166A1 - 一种改性沥青改性剂掺量的设计参考值定量方法 - Google Patents

一种改性沥青改性剂掺量的设计参考值定量方法 Download PDF

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WO2020119166A1
WO2020119166A1 PCT/CN2019/101149 CN2019101149W WO2020119166A1 WO 2020119166 A1 WO2020119166 A1 WO 2020119166A1 CN 2019101149 W CN2019101149 W CN 2019101149W WO 2020119166 A1 WO2020119166 A1 WO 2020119166A1
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modified asphalt
modifier
dosage
reference value
unsaturation
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French (fr)
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梁波
刘正春
郑健龙
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Central South University
Changsha University of Science and Technology
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Central South University
Changsha University of Science and Technology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/42—Road-making materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
    • G—PHYSICS
    • G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
    • G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
    • G16C60/00—Computational materials science, i.e. ICT specially adapted for investigating the physical or chemical properties of materials or phenomena associated with their design, synthesis, processing, characterisation or utilisation

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  • the invention belongs to the technical field of pavement construction, and in particular relates to a quantitative method for design reference value of the amount of modified asphalt modifier.
  • thermoplastic styrene-butadiene-styrene (Styrene-butadiene-styrene block copolymer) (SBS) is the most widely used polymer, which can comprehensively improve road performance.
  • SBS thermoplastic styrene-butadiene-styrene
  • the thermodynamic incompatibility between SBS and matrix asphalt leads to generally poor storage stability of SBS modified asphalt, which is mainly due to unstable physical cross-linking between molecules, this physical cross-linking mainly depends on van der Waals force, Hydrogen bonding and dispersion forces are maintained.
  • crosslinking with molecular sulfur is the most common method. It is generally believed that sulfur not only produces chemical bonds between SBS chains, but also produces chemical bonds between SBS and asphalt molecules through sulfides or polysulfides.
  • the amount of SBS corresponding to the point where the phase transition occurs has also become a sudden change in the quality of modified asphalt.
  • the existing design of modifier content is mainly designed to meet the three major indicators of conventional penetration, softening point and low temperature ductility. Adjustment and determination are mainly based on apparent performance testing and experience summary. For example, the parameters for adding sulfur to different modified asphalts have been used for more than 40 years. Therefore, it is urgent to develop a quantitative parameter that can quantitatively reveal the interaction mechanism between asphalt molecules and modifiers, and the optimization of asphalt modification process, especially the design of modifier dosage.
  • the object of the present invention is to provide a quantitative method for designing reference value of the modified asphalt modifier dosage, and to quantitatively determine the modifier in the modified asphalt from the dispersed phase to the continuous phase by potentiometric titration
  • the inflection point is used to determine the reference value of modifier content, so as to quantitatively determine the influence of modifier content on the performance of modified asphalt.
  • the embodiment of the present invention provides a method for quantifying the design reference value of the modified asphalt modifier dosage, which includes the following steps:
  • the modifier dosage in the modified asphalt sample is 0-20 wt%, and the modifier dosage changes in a linear gradient.
  • the modifier is a polymer material containing ethylenic bonds or acetylene bonds.
  • the modifier is one or more of SBS, SBR, and polyisoprene rubber.
  • the step (1) is as follows:
  • the step (2) is as follows:
  • step S2 Titrate the solution obtained in step S1 with a sodium thiosulfate solution with a concentration of 0.1 to 2M, determine the end point of titration by potentiometric titration, and determine the volume V 1 of the consumed sodium thiosulfate in mL;
  • the unsaturation Y of the modified asphalt sample is obtained by formula (1);
  • C is the concentration of sodium thiosulfate in mol/L
  • 126.9 is the molar mass of iodine molecule in g/mol
  • W is the mass of the modified asphalt sample in g.
  • the step (3) is as follows:
  • the value of the abscissa corresponding to the inflection point O is the design reference value of the modifier content in the modified asphalt.
  • the embodiment of the present invention tracks the quantitative effect of different modifier contents on the unsaturation of the modified asphalt sample through the electrochemical potential titration method, and establishes a method for detecting the unsaturation inflection point in the modified asphalt sample, which is used in the asphalt modification formula.
  • the design reference value of modifier provides quantitative calculation basis.
  • the embodiment of the present invention provides a quantitative method for designing reference value of modified asphalt modifier dosage, based on potentiometric titration to determine the series of modified asphalt unsaturation changes with modifier dosage, and then draw modified asphalt unsaturated The curve of the degree of change with the amount of modifier added, and further through data fitting analysis to obtain the inflection point of the unsaturation of modified asphalt with the amount of modifier in the asphalt, and the amount of modifier added in the process design of modified asphalt Reference value.
  • the embodiments of the present invention directly reflect the modification of modified asphalt in essence by more accurately measuring the effect of the modifier dosage on the unsaturated content of modified asphalt.
  • the chemical interaction mechanism between the agent and the base asphalt and can also directly track the process of the modifier in the modified asphalt from the independent phase to the continuous phase, has a positive significance for obtaining high-performance modified asphalt.
  • FIG. 1 is a schematic diagram of a quantitative method for reference value of modified asphalt modifier dosage according to an embodiment of the present invention.
  • FIG. 2 is a graph showing the variation of the degree of unsaturation with the amount of modifier in Example 1 of the present invention and the linear fitting result of the partition.
  • FIG. 3 is a graph showing the variation of the degree of unsaturation with the amount of modifier in Example 2 of the present invention and the linear fitting result of the partition.
  • FIG. 4 is a graph showing the variation of the degree of unsaturation with the amount of modifier in Example 3 of the present invention and the linear fitting result of the partition.
  • the embodiment of the present invention provides a method for quantifying the design reference value of the modified asphalt modifier dosage, which includes the following steps:
  • step (3) Titrate the solution obtained in step (2) with a sodium thiosulfate solution with a concentration of 0.1 to 2M, determine the end point of titration by potentiometric titration, and determine the volume V 1 of the consumed sodium thiosulfate in mL;
  • C is the concentration of sodium thiosulfate, unit mol/L, 126.9 is the molar mass of iodine molecule, unit g/mol, W is the mass of the modified asphalt sample, unit is g;
  • the intersection point of the straight line L 1 and the straight line L 2 is determined as the inflection point O of the change of unsaturation with the modifier content, and the abscissa value corresponding to the inflection point O is the design reference of the modifier content in the modified asphalt value.
  • the modifier can generate a continuous corresponding amount of modifier in the asphalt as a reference standard, and the reference standard is defined as a high content; below the reference Standard, defined as low dosing. Different asphalt or different modifiers have different reference standards.
  • the low modifier content region (range of 0-10%) refers to that the modifier low dosage region meets two conditions.
  • the modifier dosage corresponds to the low dosage, That is lower than the above-mentioned reference standard, on the other hand, the amount of modifier is still in the range of 0-10%.
  • the modifier high-doping area (in the range of 6-20%) means that the modifier high-doping area satisfies two conditions.
  • the modifier doping amount corresponds to the high doping amount. That is higher than the above-mentioned reference standard, on the other hand, the modifier dosage should also be in the range of 6-20%.
  • the potentiometric titration method refers to the method of determining the end point of titration by measuring the potential change during the titration process. Specifically, the potentiometric titration method relies on the sudden jump of the electrode potential to indicate the end point of the titration. Before and after the end point is reached, the concentration of the ions to be measured in the drop often changes by an order of magnitude, causing a jump in the potential. The content of the measured component is still calculated by the amount of titrant consumed. Therefore, in the examples of this application, it is determined by the potential titration method The unsaturation of each modified asphalt sample is more accurate.
  • the potentiometric titration method does not need to accurately measure the electrode potential value, it considers the potential mutation, so the influence of temperature and liquid junction potential on the titration end point can be ignored, so the method of the embodiment of the present application has better anti-interference Ability; furthermore, the color of asphalt is black, and the end point of titration cannot be judged by color.
  • the potentiometric titration method of the embodiment of the present application is not affected by the color change.
  • the amount of modifier in the modified asphalt sample is 0-20wt%, and the amount of modifier changes in a linear gradient.
  • the unit of M is mol/L (mole per liter).
  • Adopt No. 70 base asphalt 1 provided by a well-known enterprise, according to the preparation process of the embodiment of the present invention, weigh a certain amount of base asphalt and 1g of furfural to extract oil, heat to 175°C ⁇ 180°C, first at a shear rate of 500r/min Then add SBS modifier to maintain the temperature at 175°C ⁇ 180°C, then adjust the shear speed to 3000r/min and shear for 30min; the sample is transferred to a blender and stirred at 500r/min for 4h, and then the stabilizer 0.1g sulfur is added The powder is mixed and stirred for 3 hours to complete the modification.
  • the modified asphalt prepared is controlled by a single variable method, so that all modified asphalt samples are only different in the amount of SBS modifier. The formula is shown in Table 1.
  • step (3) Titrate the solution obtained in step (2) with a 0.2 M sodium thiosulfate solution, determine the end point of titration by potentiometric titration, and determine the volume V 1 of the consumed sodium thiosulfate in mL, as shown in the table 2 shown;
  • C is the concentration of sodium thiosulfate 0.2mol/L
  • W is the mass of the modified asphalt sample 2.0g
  • the intersection point of the straight line L 1 and the straight line L 2 is determined as the inflection point O where the degree of unsaturation changes with the amount of modifier.
  • the abscissa value corresponding to the inflection point O is 5.85%, which is the modifier in the modified asphalt Dosage design reference value.
  • Use No. 90 base asphalt 2 provided by a well-known enterprise, according to the preparation process of the embodiment of the present invention, weigh a certain amount of base asphalt and 1 g of furfural to extract the oil, heat to 175 °C ⁇ 180 °C, first at a shear rate of 500r/min Then add SBS modifier to maintain the temperature at 175°C ⁇ 180°C, then adjust the shear speed to 3000r/min and shear for 30min; the sample is transferred to a blender and stirred at 500r/min for 4h, and then the stabilizer 0.1g sulfur is added The powder is mixed and stirred for 3 hours to complete the modification.
  • the modified asphalt prepared is controlled by a single variable method, so that all modified asphalt samples are different in the amount of SBS modifier. The formula is shown in Table 3.
  • step (3) Titrate the solution obtained in step (2) with a sodium thiosulfate solution with a concentration of 0.1998M, determine the end point of titration by potentiometric titration, and determine the volume V 1 of the consumed sodium thiosulfate in mL, as shown in the table 4 shown;
  • C is the concentration of sodium thiosulfate 0.1998mol/L
  • W is the mass of the modified asphalt sample 2.0g
  • the intersection point of the straight line L 1 and the straight line L 2 is determined as the inflection point O where the degree of unsaturation changes with the amount of modifier.
  • the abscissa value corresponding to the inflection point O is 5.6%, which is the modifier in the modified asphalt Dosage design reference value.
  • No. 70 base asphalt 3 provided by a well-known enterprise, according to the preparation process of the embodiment of the present invention, weigh a certain amount of base asphalt and 1g of furfural to extract the oil, heat to 175°C ⁇ 180°C, first at a shear rate of 500r/min Then add SBS modifier to maintain the temperature at 175°C ⁇ 180°C, then adjust the shear speed to 3000r/min and shear for 30min; the sample is transferred to a blender and stirred at 500r/min for 4h, and then the stabilizer 0.1g sulfur is added Powder, stirring for 3h to complete the modification.
  • the prepared modified asphalt is controlled by a single variable method, so that all modified asphalt samples are only different in the amount of SBS modifier. The formula is shown in Table 5.
  • the design reference value quantitative method using the modified asphalt modifier dosage of the present invention has the following specific steps:
  • step (3) Titrate the solution obtained in step (2) with a sodium thiosulfate solution with a concentration of 0.1978M, determine the end point of titration by potentiometric titration, and determine the volume V 1 of the sodium thiosulfate consumed, the unit is mL, as shown in the table 6 shown;
  • C is the concentration of sodium thiosulfate 0.1978mol/L
  • W is the mass of the modified asphalt sample 2.0g
  • the intersection point of the straight line L 1 and the straight line L 2 is determined as the inflection point O where the degree of unsaturation changes with the amount of modifier.
  • the abscissa value corresponding to the inflection point O is 5.05%, which is the modifier in the modified asphalt Dosage design reference value.

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Abstract

一种改性沥青改性剂掺量的设计参考值定量方法，属于路面施工技术领域，基于电位滴定的确定系列改性沥青不饱和度随改性剂掺量的变化，进而绘制改性沥青不饱和度随改性剂掺量变化的曲线，进一步通过数据拟合分析获得改性沥青不饱和度随沥青中改性剂掺量变化的拐点，建立改性沥青的工艺设计中改性剂添加掺量的参考值。通过较为准确地测定改性剂的掺量对改性沥青分子不饱和键的影响，从本质上直接体现改性沥青中改性剂与基质沥青之间的化学作用机理，并且还可以直接跟踪改性沥青中改性剂从独立相转变为连续相的过程，对获得高性能的改性沥青具有积极的意义。

Description

一种改性沥青改性剂掺量的设计参考值定量方法
相关申请的交叉引用
本申请基于申请号为201811525955.3、申请日为2018年12月13日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明属于路面施工技术领域，具体涉及一种改性沥青改性剂掺量的设计参考值定量方法。
背景技术
随着沥青在道路建设中的广泛应用，特别是聚合物改性沥青能显著改善路面的老化性能、耐久性、永久变形和热敏感性。其中，热塑性苯乙烯-丁二烯-苯乙烯(Styrene-butadiene-styrene block copolymer，简称SBS)是应用最广泛的聚合物，可以综合改善路面性能。然而，SBS与基质沥青间的热力学上不相容性导致SBS改性沥青的储存稳定性普遍较差，这主要是由于分子间不稳定的物理交联，这种物理交联主要靠范德华力、氢键和色散力来维持。为了提高贮存稳定性，用分子硫交联是最普遍的方法。人们普遍认为，硫不仅在SBS链之间产生化学键合，而且通过硫化物或多硫化物在SBS和沥青分子之间产生化学键合。
目前，已有学者已经在SBS和SBS/硫改性沥青的改性机理方面做了大量的研究工作。硫的加入大大改善了SBS改性沥青的流变性能，通过荧光显微镜观察SBS/沥青共混物和SBS/沥青/硫共混物的形态差异，发现SBS/沥青/硫共混物为连续的富聚合物相，SBS/沥青共混物为富聚合物相。结果表明，硫促进了SBS改性沥青的连续聚合网络的形成，进一步提高了SBS改性沥青的性能。通过沥青的性能和微观结构观察提供了交联反应的定性证据。在沥青改性过程中，硫 分子硫化的确切反应机理尚不明确，不足以指导SBS改性沥青的加工工艺设计。SBS无疑是当今较好的聚合物改性剂，改性过程中SBS与基质沥青或硫之间的化学反应将导致碳-碳双键的减少，因为基质沥青里面以及SBS分子上孤立的碳-碳双键在反应过程中容易受到攻击。因此，双键的变化将是化学交联的直接证据。已有研究表明，随着SBS掺量的增加，SBS在沥青中的状态从被基质沥青包裹的点状分散性分布进入到片状分布，最后反转成为包裹沥青的连续相。在相转变发生点所对应的SBS掺量也成为改性沥青质量突变点，然而现有的改性剂掺量设计主要通过满足常规的针入度、软化点及低温延度三大指标设计来进行调节确定，主要建立在表观性能测试和经验总结上。例如，在不同改性沥青中添加硫的参数已经使用了40多年。因此，发展一种能定量揭示沥青分子与改性剂之间的相互作用机制，沥青改性工艺优化的定量参数，特别是改性剂掺量的设计迫在眉睫。
发明内容
针对现有技术的不足，本发明的目的在于提供一种改性沥青改性剂掺量的设计参考值定量方法，利用电位滴定法定量确定改性沥青中改性剂从分散相转变为连续相的拐点，通过拐点确定改性剂掺量参考值，从而定量确定改性剂掺量对改性沥青性能的影响。
本发明实施例提供一种改性沥青改性剂掺量的设计参考值定量方法，包括以下步骤：
(1)制备一系列不同改性剂掺量的改性沥青样品；
(2)利用电位滴定法确定每一改性沥青样品的不饱和度；
(3)通过数据拟合，获得改性沥青不饱和度随改性剂掺量发生变化的拐点；
(4)通过拐点确定改性剂掺量的参考值。
作为优选，所述改性沥青样品中改性剂掺量为0～20wt％，改性剂掺量成线性梯度变化。
作为优选，所述改性剂为含烯键、炔键的高分子材料。
作为优选，所述改性剂为SBS、SBR、聚异戊二烯橡胶中的一种或多种。
作为优选，所述步骤(1)具体如下：
配制若干组不同改性剂掺量的改性沥青样品四氢呋喃溶液，每组所取改性沥青样品的质量为0.5～10g，四氢呋喃的加入量为5～100mL。
作为优选，所述步骤(2)具体如下：
S1、向改性沥青样品的四氢呋喃溶液中加入10～30mL，浓度为0.01～1M的韦氏试剂，在30～50℃下反应8～24h；然后加入5～30mL，浓度为10～1000g/L的碘化钾溶液，反应1～60min；
S2、用浓度为0.1～2M的硫代硫酸钠溶液对步骤S1所得溶液进行滴定，通过电位滴定法判断滴定终点，确定消耗的硫代硫酸钠的体积V 1，单位为mL；
S3、配置四氢呋喃空白溶液，重复S1和S2，获得空白溶液滴定所消耗的硫代硫酸钠体积V 0，单位为mL；
S4、通过公式(1)获得改性沥青样品的不饱和度Y；
Figure PCTCN2019101149-appb-000001
式(1)中C为硫代硫酸钠的浓度，单位mol/L，126.9为碘分子摩尔质量，单位g/mol，W为改性沥青样品的质量，单位为g。
作为优选，所述步骤(3)具体如下：
a)以改性剂掺量为横坐标，改性沥青样品的不饱和度为纵坐标绘制曲线；
b)在不饱和度线性增长的改性剂低掺量区域(0～10％范围)拟合一条直线L 1，在不饱和度进入平台期的改性剂高掺量区域(6～20％范围)拟合一条直线L 2；
c)直线L 1与直线L 2的交叉点确定为不饱和度随改性剂掺量变化的拐点O。
作为优选，所述步骤(4)中，拐点O所对应的横坐标值即为改性沥青中改性剂掺量设计参考值。
本发明实施例的原理：改性沥青制备过程中伴随着碳-碳双键、碳-碳三键的变化，通过卤素与C＝C双键、C≡C三键的化学计量反应来检测，本发明实施例通过电化学电位滴定方法跟踪不同改性剂掺量对改性沥青样品不饱和度的定量影响，建立一种改性沥青样品中不饱和度拐点检测方法，为沥青改性配方中改性剂的设计参考值提供定量计算依据。
与现有技术相比，本发明实施例的有益技术效果为：
本发明实施例提供一种改性沥青改性剂掺量的设计参考值定量方法，基于电位滴定的确定系列改性沥青不饱和度随改性剂掺量的变化，进而绘制改性沥青不饱和度随改性剂掺量变化的曲线，进一步通过数据拟合分析获得改性沥青不饱和度随沥青中改性剂掺量变化的拐点，建立改性沥青的工艺设计中改性剂添加掺量的参考值。与常规改性沥青改性剂掺量设计方法相比，本发明实施例通过较为准确地测定改性剂的掺量对改性沥青不饱和度的影响，从本质上直接体现改性沥青中改性剂与基质沥青之间的化学作用机理，并且还可以直接跟踪改性沥青中改性剂从独立相转变为连续相的过程，对获得高性能的改性沥青具有积极的意义。
附图说明
图1为本发明实施例改性沥青改性剂掺量参考值定量方法示意图。
图2为本发明实例1中不饱和度随改性剂掺量变化的曲线及分区线性拟合结果图。
图3为本发明实例2中不饱和度随改性剂掺量变化的曲线及分区线性拟合结果图。
图4为本发明实例3中不饱和度随改性剂掺量变化的曲线及分区线性拟合结果图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部实施例，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例提供一种改性沥青改性剂掺量的设计参考值定量方法，包括以下步骤：
(1)配制若干组不同改性剂掺量的改性沥青样品四氢呋喃溶液，每组所取改性沥青样品的质量为0.5～10g，四氢呋喃的加入量为5～100mL；
(2)向改性沥青样品的四氢呋喃溶液中加入10～30mL，浓度为0.01～1M的韦氏试剂，在30～50℃下反应8～24h；然后加入5～30mL，浓度为10～1000g/L的碘化钾溶液，反应1～60min；
(3)用浓度为0.1～2M的硫代硫酸钠溶液对步骤(2)所得溶液进行滴定，通过电位滴定法判断滴定终点，确定消耗的硫代硫酸钠的体积V 1，单位为mL；
(4)配置四氢呋喃空白溶液，重复步骤(2)和(3)，获得空白溶液滴定所消耗的硫代硫酸钠体积V 0，单位为mL；
(5)通过公式(1)获得改性沥青样品的不饱和度Y；
Figure PCTCN2019101149-appb-000002
式(1)中C为硫代硫酸钠的浓度，单位mol/L，126.9为碘分子摩尔质量，单位g/mol，W为改性沥青样品的质量，单位为g；
(6)以改性剂掺量为横坐标，改性沥青样品的不饱和度为纵坐标绘制曲线，如图1所示，在不饱和度线性增长的改性剂低掺量区域(0～10％范围)拟合一条直线L 1，在不饱和度进入平台期的改性剂高掺量区域(6～20％范围)拟合一条直线L 2；
(7)直线L 1与直线L 2的交叉点确定为不饱和度随改性剂掺量变化的拐点O，拐点O所对应的横坐标值即为改性沥青中改性剂掺量设计参考值。
需要说明的是，在工艺确定的情况下，以改性剂在沥青中能够生成连续相对应的改性剂掺量为参照标准，高于该参照标准的定义为高掺量；低于该参照标准的，定义为低掺量。不同的沥青，或者是不同的改性剂，对应的参照标准不同。
所述的改性剂低掺量区域(0～10％范围)，指的是，改性剂低掺量区域满足两方面条件，一方面是该改性剂掺量对应的是低掺量，即低于上述的参照标准，另一方面是改性剂掺量还要位于0～10％范围。
所述的改性剂高掺量区域(6～20％范围)，指的是，改性剂高掺量区域满足两方面条件，一方面是该改性剂掺量对应的是高掺量，即高于上述的参照标准，另一方面是改性剂掺量还要位于6～20％范围。
需要说明的是，所述的电位滴定法，指的是在滴定过程中通过测量电位变 化以确定滴定终点的方法，具体地，电位滴定法是靠电极电位的突跃来指示滴定终点，在滴定到达终点前后，滴液中的待测离子浓度往往呈数量级变化，引起电位的突跃，被测成分的含量仍然通过消耗滴定剂的量来计算，因此，本申请实施例中通过电位滴定法确定的每一改性沥青样品的不饱和度比较准确。由于电位滴定法不需要准确的测量电极电位值，考虑的是电位的突变，因此，温度、液体接界电位等对滴定终点的影响可以忽略，故本申请实施例的方法具有较好的抗干扰能力；再者，沥青的颜色本身呈黑色，无法通过颜色来判断滴定终点，本申请实施例的电位滴定法不受颜色变化影响。
改性沥青样品中改性剂掺量为0～20wt％，改性剂掺量成线性梯度变化。
改性剂为含烯键(C＝C双键)、炔键(C≡C三键)的高分子材料；改性剂为SBS、SBR(Styrene Butadiene Rubber，丁苯橡胶)、聚异戊二烯橡胶中的一种或多种。
下面结合具体实施例和附图对本发明进行进一步说明。
需要说明的是，本申请实施例中，M的单位为mol/L(摩尔每升)。
实施例1
采用某知名企业提供的70号基质沥青1，按照本发明实施例制备工艺，称取一定量的基质沥青及1g糠醛抽出油，加热到175℃～180℃，先在500r/min的剪切速度下加入SBS改性剂，维持温度在175℃～180℃，随后将剪速调至3000r/min，剪切30min；样品转至搅拌机，以500r/min转速搅拌4h，再添加稳定剂0.1g硫粉，搅拌3h改性完成；制备的改性沥青采用单一变量法控制，使得所有改性沥青样品只是SBS改性剂掺量不同，其配方按照表1所示。
表1 实施例1中改性沥青的配方
Figure PCTCN2019101149-appb-000003
Figure PCTCN2019101149-appb-000004
采用本发明实施例改性沥青改性剂掺量的设计参考值定量方法，具体步骤如下：
(1)配制若干组不同改性剂掺量的改性沥青样品四氢呋喃溶液，每组所取改性沥青样品的质量为2.0g，四氢呋喃的加入量为50mL；
(2)向改性沥青样品的四氢呋喃溶液中加入15mL，浓度为0.1M的韦氏试剂，在45℃下反应8h；然后加入10mL，浓度为10g/L的碘化钾溶液，反应5min；
(3)用浓度为0.2M的硫代硫酸钠溶液对步骤(2)所得溶液进行滴定，通过电位滴定法判断滴定终点，确定消耗的硫代硫酸钠的体积V 1，单位为mL，如表2所示；
(4)配置四氢呋喃空白溶液50mL，重复步骤(2)和(3)，获得空白溶液滴定所消耗的硫代硫酸钠体积V 0为24.4350mL；
(5)通过公式(1)获得改性沥青样品的不饱和度Y，如表2所示；
Figure PCTCN2019101149-appb-000005
式(1)中C为硫代硫酸钠的浓度0.2mol/L，W为改性沥青样品的质量2.0g；
(6)以改性剂掺量为横坐标，改性沥青样品的不饱和度为纵坐标绘制曲线，如图2所示，在不饱和度线性增长的改性剂低掺量区域(0～4.5％范围)拟合一条 直线L 1，在不饱和度进入平台期的改性剂高掺量区域(7.5～10％范围)拟合一条直线L 2；
(7)直线L 1与直线L 2的交叉点确定为不饱和度随改性剂掺量变化的拐点O，拐点O所对应的横坐标值为5.85％，即为改性沥青中改性剂掺量设计参考值。
表2 SBS改性基质沥青一不饱和度电位滴定结果
SBS掺量/％ 滴定体积(V 1)/mL 不饱和度Y(A)
0.0 8.4011 20.3470
0.5 8.1956 20.6078
1.0 8.0154 20.8365
1.5 7.8395 21.0597
2.0 7.6563 21.2922
2.5 7.4713 21.5269
3.0 7.2982 21.7466
3.5 7.1251 21.9663
4.0 6.9575 22.1789
4.5 6.7975 22.3820
5.0 6.6363 22.5866
5.5 6.4727 22.7942
6.0 6.4068 22.8778
6.5 6.3418 22.9603
7.0 6.2388 23.0910
7.5 6.1426 23.2131
8.0 6.0869 23.2837
8.5 6.0515 23.3287
9.0 6.0170 23.3724
9.5 5.9631 23.4408
10.0 5.9131 23.5043
实施例2
采用某知名企业提供的90号基质沥青2，按照本发明实施例制备工艺，称取一定量的基质沥青及1g糠醛抽出油，加热到175℃～180℃，先在500r/min的剪切速度下加入SBS改性剂，维持温度在175℃～180℃，随后将剪速调至3000r/min，剪切30min；样品转至搅拌机，以500r/min转速搅拌4h，再添加稳 定剂0.1g硫粉，搅拌3h改性完成，制备的改性沥青采用单一变量法控制，使得所有改性沥青样品只是SBS改性剂掺量不同，其配方按照表3所示。
表3 实施例2中改性沥青的配方
Figure PCTCN2019101149-appb-000006
采用本发明实施例改性沥青改性剂掺量的设计参考值定量方法，具体步骤如下：
(1)配制若干组不同改性剂掺量的改性沥青样品四氢呋喃溶液，每组所取改 性沥青样品的质量为2.0g，四氢呋喃的加入量为55mL；
(2)向改性沥青样品的四氢呋喃溶液中加入15mL，浓度为0.2M的韦氏试剂，在35℃下反应12h；然后加入10mL，浓度为10g/L的碘化钾溶液，反应3min；
(3)用浓度为0.1998M的硫代硫酸钠溶液对步骤(2)所得溶液进行滴定，通过电位滴定法判断滴定终点，确定消耗的硫代硫酸钠的体积V 1，单位为mL，如表4所示；
(4)配置四氢呋喃空白溶液55mL，重复步骤(2)和(3)，获得空白溶液滴定所消耗的硫代硫酸钠体积V 0为24.8350mL；
(5)通过公式(1)获得改性沥青样品的不饱和度Y，如表4所示；
Figure PCTCN2019101149-appb-000007
式(1)中C为硫代硫酸钠的浓度0.1998mol/L，W为改性沥青样品的质量2.0g；
(6)以改性剂掺量为横坐标，改性沥青样品的不饱和度为纵坐标绘制曲线，如图3所示，在不饱和度线性增长的改性剂低掺量区域(0～5％范围)拟合一条直线L 1，在不饱和度进入平台期的改性剂高掺量区域(7.5～12％范围)拟合一条直线L 2；
(7)直线L 1与直线L 2的交叉点确定为不饱和度随改性剂掺量变化的拐点O，拐点O所对应的横坐标值为5.6％，即为改性沥青中改性剂掺量设计参考值。
表4 SBS改性基质沥青一不饱和度电位滴定结果
SBS掺量/％ 滴定体积(V 1)/mL 不饱和度Y
0 8.8692 20.2403
0.5 8.7037 20.4501
1 8.5449 20.6515
1.5 8.3823 20.8576
2 8.2163 21.068
2.5 8.0563 21.2709
3 7.8999 21.4691
3.5 7.7375 21.675
4 7.5886 21.8638
4.5 7.4268 22.0689
5 7.2660 22.2728
5.5 7.1823 22.3789
6 7.0703 22.5209
6.5 6.9991 22.6111
7 6.9172 22.7149
7.5 6.8610 22.7862
8 6.8186 22.8399
8.5 6.7861 22.8811
9 6.7611 22.9129
9.5 6.7211 22.9635
10 6.6913 23.0013
10.5 6.6536 23.0491
11 6.6128 23.1008
11.5 6.5773 23.1459
12 6.5353 23.1991
实施例3
采用某知名企业提供的70号基质沥青3，按照本发明实施例制备工艺，称取一定量的基质沥青及1g糠醛抽出油，加热到175℃～180℃，先在500r/min的剪切速度下加入SBS改性剂，维持温度在175℃～180℃，随后将剪速调至3000r/min，剪切30min；样品转至搅拌机，以500r/min转速搅拌4h，再添加稳定剂0.1g硫粉，搅拌3h改性完成。制备的改性沥青采用单一变量法控制，使得所有改性沥青样品只是SBS改性剂掺量不同，其配方按照表5所示。
表5 实施例3中改性沥青的配方
Figure PCTCN2019101149-appb-000008
Figure PCTCN2019101149-appb-000009
采用本发明改性沥青改性剂掺量的设计参考值定量方法，具体步骤如下：
(1)配制若干组不同改性剂掺量的改性沥青样品四氢呋喃溶液，每组所取改性沥青样品的质量为2.0g，四氢呋喃的加入量为50mL；
(2)向改性沥青样品的四氢呋喃溶液中加入15mL，浓度为0.1M的韦氏试剂，在50℃下反应4h；然后加入10mL，浓度为10g/L的碘化钾溶液，反应8min；
(3)用浓度为0.1978M的硫代硫酸钠溶液对步骤(2)所得溶液进行滴定，通过电位滴定法判断滴定终点，确定消耗的硫代硫酸钠的体积V 1，单位为mL，如表6所示；
(4)配置四氢呋喃空白溶液50mL，重复步骤(2)和(3)，获得空白溶液滴定所消耗的硫代硫酸钠体积V 0为24.6350mL；
(5)通过公式(1)获得改性沥青样品的不饱和度Y，如表6所示；
Figure PCTCN2019101149-appb-000010
式(1)中C为硫代硫酸钠的浓度0.1978mol/L，W为改性沥青样品的质量2.0g；
(6)以改性剂掺量为横坐标，改性沥青样品的不饱和度为纵坐标绘制曲线，如图4所示，在不饱和度线性增长的改性剂低掺量区域(0～4.5％范围)拟合一条直线L 1，在不饱和度进入平台期的改性剂高掺量区域(8～15％范围)拟合一条直线L 2；
(7)直线L 1与直线L 2的交叉点确定为不饱和度随改性剂掺量变化的拐点O，拐点O所对应的横坐标值为5.05％，即为改性沥青中改性剂掺量设计参考值。
表6 SBS改性基质沥青一不饱和度电位滴定结果
SBS掺量/％ 滴定体积(V 1)/mL 不饱和度Y
0 8.3408 20.4499
0.5 8.1801 20.6516
1 8.0160 20.8575
1.5 7.8484 21.0679
2 7.6868 21.2707
2.5 7.5289 21.4689
3 7.3647 21.6749
3.5 7.2141 21.8639
4 7.0504 22.0694
4.5 6.8886 22.2725
5 6.8040 22.3786
6 6.6905 22.5211
7 6.5391 22.7111
8 6.4564 22.8149
9 6.3836 22.9062
10 6.3010 23.0099
11 6.2301 23.0989
12 6.1711 23.1729
13 6.0990 23.2635
14 6.0290 23.3513
15 5.9511 23.4491
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上 述实施例。对于本技术领域的技术人员来说，在不脱离本发明技术构思前提下所得到的改进和变换也应视为本发明的保护范围。

Claims (8)

  1. 一种改性沥青改性剂掺量的设计参考值定量方法，其特征在于，包括以下步骤：
    (1)制备一系列不同改性剂掺量的改性沥青样品；
    (2)利用电位滴定法确定每一改性沥青样品的不饱和度；
    (3)通过数据拟合，获得改性沥青不饱和度随改性剂掺量发生变化的拐点；
    (4)通过拐点确定改性剂掺量的参考值。
  2. 根据权利要求1所述改性沥青改性剂掺量的设计参考值定量方法，其特征在于，所述改性沥青样品中改性剂掺量为0～20wt％，改性剂掺量成线性梯度变化。
  3. 根据权利要求1所述改性沥青改性剂掺量的设计参考值定量方法，其特征在于，所述改性剂为含烯键、炔键的高分子材料。
  4. 根据权利要求3所述改性沥青改性剂掺量的设计参考值定量方法，其特征在于，所述改性剂为SBS、SBR、聚异戊二烯橡胶中的一种或多种。
  5. 根据权利要求1所述改性沥青改性剂掺量的设计参考值定量方法，其特征在于，所述步骤(1)具体如下：
    配制若干组不同改性剂掺量的改性沥青样品四氢呋喃溶液，每组所取改性沥青样品的质量为0.5～10g，四氢呋喃的加入量为5～100mL。
  6. 根据权利要求1所述改性沥青改性剂掺量的设计参考值定量方法，其特征在于，所述步骤(2)具体如下：
    S1、向改性沥青样品的四氢呋喃溶液中加入10～30mL，浓度为0.01～1M的韦氏试剂，在30～50℃下反应8～24h；然后加入5～30mL，浓度为10～1000g/L的碘化钾溶液，反应1～60min；
    S2、用浓度为0.1～2M的硫代硫酸钠溶液对步骤S1所得溶液进行滴定，通过电位滴定法判断滴定终点，确定消耗的硫代硫酸钠的体积V 1，单位为mL；
    S3、配置四氢呋喃空白溶液，重复S1和S2，获得空白溶液滴定所消耗的硫代硫酸钠体积V 0，单位为mL；
    S4、通过公式(1)获得改性沥青样品的不饱和度Y；
    Figure PCTCN2019101149-appb-100001
    式(1)中C为硫代硫酸钠的浓度，单位mol/L，126.9为碘分子摩尔质量，单位g/mol，W为改性沥青样品的质量，单位为g。
  7. 根据权利要求1所述改性沥青改性剂掺量的设计参考值定量方法，其特征在于，所述步骤(3)具体如下：
    a)以改性剂掺量为横坐标，改性沥青样品的不饱和度为纵坐标绘制曲线；
    b)在不饱和度线性增长的改性剂低掺量区域(0～10％范围)拟合一条直线L 1，在不饱和度进入平台期的改性剂高掺量区域(6～20％范围)拟合一条直线L 2；
    c)直线L 1与直线L 2的交叉点确定为不饱和度随改性剂掺量变化的拐点O。
  8. 根据权利要求1所述改性沥青改性剂掺量的设计参考值定量方法，其特征在于，所述步骤(4)中，拐点O所对应的横坐标值即为改性沥青中改性剂掺量设计参考值。
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