WO2019242556A1 - 石墨烯复合橡胶沥青改性剂及其制备方法和应用 - Google Patents

石墨烯复合橡胶沥青改性剂及其制备方法和应用 Download PDF

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WO2019242556A1
WO2019242556A1 PCT/CN2019/091060 CN2019091060W WO2019242556A1 WO 2019242556 A1 WO2019242556 A1 WO 2019242556A1 CN 2019091060 W CN2019091060 W CN 2019091060W WO 2019242556 A1 WO2019242556 A1 WO 2019242556A1
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graphene
powder
asphalt modifier
rubber
composite rubber
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French (fr)
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田植群
沈培康
翁晓娜
归立发
梁立喆
李卫庆
尹诗斌
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Guangxi Zhengtong Engineering And Technology Co Ltd
Guangxi University
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Guangxi Zhengtong Engineering And Technology Co Ltd
Guangxi University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of asphalt modifiers, in particular to a graphene composite rubber asphalt modifier, and a preparation method and application thereof.
  • Asphalt pavement has the characteristics of comfortable driving, quiet driving and convenient maintenance. At present, more than 95% of the roads in the world are paved with asphalt pavement.
  • the important material composition of asphalt pavement ranges from the original residual oil, experienced ordinary asphalt, heavy traffic asphalt to current usage. With more than 50% of modified asphalt, with the rapid development of rapid economic development, the traffic load has increased rapidly.
  • Asphalt pavements constructed of ordinary asphalt or heavy traffic asphalt have various problems, such as cracks, ruts, and deformation due to insufficient high-temperature performance. Many problems such as cracking of the pavement caused by insufficient low temperature performance can no longer meet the requirements of practical use.
  • Rubber asphalt is an asphalt cementing material formed by processing rubber powder from waste tires and then fully blending with matrix asphalt in a certain proportion.
  • Graphene is a new type of functional material.
  • the carbon atoms in the structure are connected by a strong ⁇ bond, which makes the graphene sheet have excellent mechanical properties.
  • there are two methods for preparing two-dimensional graphene one is a top-down method, which is to obtain graphene from the decomposition of graphite or carbon nanotubes with a higher structure than graphene, such as mechanical peeling, insertion Layer stripping method, solvent liquid phase stripping method and redox method; the other is a bottom-up method, which uses a carbon source (small molecules such as methane, CO, alcohol, etc.) with a lower structure than graphene to pass CVD,
  • Graphene is prepared by arc discharge, solvothermal method, and the like. The performance of graphene in specific applications is closely related to the preparation method.
  • graphene asphalts use graphene oxide, with graphene oxide as an additive, and SBS as a modifier, mixed with matrix asphalt and sulfur-containing accelerators to obtain graphene-modified asphalt; or matrix asphalt and The modifier is mixed, and then the carboxyl-modified graphene oxide is added to obtain a polyethylene-modified asphalt based on the carboxyl-modified graphene oxide.
  • graphene oxide and ethanol are dispersed ultrasonically in a certain proportion to prepare graphene oxide The sol is uniformly mixed and stirred with the medium-temperature coal pitch until the solvent in the pitch is evaporated, and the final product is obtained.
  • the prior art shows that the addition of graphene can improve asphalt adhesion, mechanical properties, high and low temperature stability, and high temperature rut resistance.
  • graphene oxide is hydrophilic and has poor compatibility with asphalt, despite functionalizing it, graphene oxide is still a two-dimensional sheet structure. It is necessary to fully disperse graphene in asphalt directly, which is technically certain. Difficulty: In the prior art, nitrogen or sulfur-doped graphene is used to increase the degree of cross-linking of graphene and asphalt, but sulfur-containing substances are not environmentally friendly. If harmful substances are released during construction, health will be endangered.
  • graphene pitch is roughly as follows: graphene is functionalized, and graphene, asphalt, and modifiers are blended and blended. This blending and blending method makes the interface performance of the three poor. Poor capacitance results in poor dispersion of graphene in asphalt, and stability cannot be guaranteed.
  • the purpose of the present invention is to provide a graphene composite rubber asphalt modifier and a preparation method and application thereof.
  • the graphene composite rubber asphalt modifier can greatly improve the compatibility and stability of rubber powder in asphalt, and can improve the Adhesive performance of modified asphalt and sand and gravel, high and low temperature stability performance, at the same time reduce the temperature of the road surface and extend the service life of the road surface.
  • the present invention provides a graphene composite rubber asphalt modifier, which includes the following components by weight: graphene powder 0.00005-0.01 parts, dispersion medium 3-23 parts, rubber powder 78-92 parts And additives of 0.05-6 parts;
  • the graphene composite rubber asphalt modifier includes the following components by weight: graphene powder 0.0001-0.005 parts, dispersion medium 5-20 parts, rubber powder 80-90 0.1-5 parts of additives, and further preferably, the graphene composite rubber asphalt modifier includes the following components by weight: 0.003 parts of graphene powder, 13 parts of dispersion medium, 85 parts of rubber powder, and additives 2.5 servings.
  • the graphene powder is selected from at least one of graphene microchips, reduced graphene oxide, and three-dimensional structure graphene; preferably, the graphene powder is three-dimensional structure graphene ; Further preferably, the specific surface area of the graphene powder is greater than or equal to 300 m2 / g; wherein the graphene microplatelets (Graphene Nanoplatelets) refer to those having less than 10 carbon layers and a lateral dimension in the range of 100 nm to 1000 microns Ultra-thin layered graphene layered body; reduced graphene oxide is the first oxidation of graphite to graphite oxide, and then to graphene oxide by exfoliation, and finally through various reduction methods (to obtain excellent performance in electrochemical, photochemical and other properties Graphene; three-dimensional structure graphene is a powder material with a honeycomb-like structure composed of two-dimensional graphene sheets, and its basic structural characteristics meet the requirements of technical standards DB 45 / T 1421-2016 and
  • the dispersion medium is selected from at least one of paraffin rubber oil, aromatic rubber oil, naphthenic rubber oil, and polycyclic aromatic rubber oil; preferably, the dispersion medium is selected At least one of a self-paraffin rubber oil, an aromatic rubber oil and a naphthenic rubber oil; further preferably, the dispersion medium is a naphthenic rubber oil.
  • the powder size of the rubber powder is 20-200 mesh; preferably, the powder size of the rubber powder is 30-150 mesh; further preferably, the powder size of the rubber powder is 40 -80 mesh.
  • the additive is selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, polyethylene, ethylene bisstearic acid amide, C9 petroleum resin, C12 petroleum resin, and silane coupling agent KH- 580, at least one of silane coupling agent KH550, silane coupling agent KH792, dodecyltrimethoxysilane, cetyltrimethoxysilane, dispersant KC163, dispersant BYK110, dispersant BYK164; preferably
  • the additive is at least one selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, polyethylene, and ethylene bisstearate; further preferably, the additive is acrylonitrile-butadiene- Copolymer of styrene. This additive is used to increase the interfacial interaction between graphene and rubber powder and to stabilize the dispersion of graphene.
  • the invention also provides a method for preparing a graphene composite rubber asphalt modifier, comprising the following steps: (1) mixing graphene powder and a dispersion medium, mechanically stirring, and then obtaining a graphene dispersion liquid through high-speed dispersion (2) The graphene dispersion liquid is densely mixed with rubber powder and additives to prepare the graphene composite rubber asphalt modifier.
  • the mass ratio of the graphene powder mixed with the dispersion medium is (0.00005-0.01): (3-23); preferably, the graphene powder The mass ratio for mixing with the dispersion medium is (0.0001-0.005): (5-20); further preferably, the mass ratio for mixing the graphene powder and the dispersion medium is 0.003: 13.
  • the high-speed dispersion is performed by dispersing the graphene powder and the liquid mixed with the dispersion medium at a temperature of 60-120 ° C for 10-60 minutes by using a high-speed shearing machine, and obtaining the solution after cooling.
  • Graphene dispersion liquid, the graphene sheet diameter distribution in the graphene dispersion liquid is 100-2000 nanometers; preferably, the high-speed shearing machine disperses the liquid after the graphene and the dispersion medium are mixed at 70 ° C.
  • the high-speed shearing machine disperses the graphene powder and the liquid mixed with the dispersion medium at 70 ° C for 35min; further preferably, the sheet diameter distribution of the graphene in the graphene dispersion liquid It is 500-1000 nm.
  • the graphene dispersion liquid, the rubber powder and the additive are added at a mass ratio of (3-23): (78-92): (0.05-6) to 200-260 ° C.
  • the mixture is kneaded for 10-60 minutes, and then cooled to prepare a graphene composite rubber asphalt modifier.
  • the graphene dispersion liquid, rubber powder and additives are (5-20): (80 -90): (0.1-5) mass mixing and kneading at 220-240 ° C for 20-50min; further preferably, in step (2), the graphene dispersion liquid, rubber powder and additives are added at 13:85: The mass ratio of 2.5 was kneaded and kneaded at 230 ° C for 35 minutes.
  • the invention also provides the application of the graphene composite rubber asphalt modifier or the preparation method thereof to the asphalt modifier.
  • the present invention has the following beneficial effects:
  • the graphene composite rubber asphalt modifier according to the present invention is selected from at least one of graphene microflakes, reduced graphene oxide, and three-dimensional structure graphene, and has better dispersibility than graphene oxide;
  • the preparation method of the graphene composite rubber asphalt modifier according to the present invention adopts a high-temperature compaction process to fully mix graphene and rubber powder, improve the modification effect of graphene, and avoid direct graphene and the matrix Insufficient dispersion caused by asphalt mixing;
  • the combination of the graphene powder and the high-temperature compaction process used in the present invention the use of less than 0.01% of the graphene powder in the asphalt can achieve better results, greatly reducing the cost of graphene-modified asphalt,
  • the graphene composite rubber asphalt modifier can greatly improve the compatibility and stability of rubber powder in asphalt, improve the bonding performance of modified asphalt and sand and gravel, high and low temperature stability, and reduce the temperature and extension of the road surface. Road life.
  • Example 1 Components and preparation method of graphene composite rubber asphalt modifier
  • the graphene composite rubber asphalt modifier components are shown below (by parts by weight)
  • the specific surface area of the three-dimensional graphene is 500 m2 / g, and the powder particle size of the rubber powder is 60 mesh.
  • the preparation method of the graphene composite rubber asphalt modifier is as follows:
  • Example 2 Components and preparation method of graphene composite rubber asphalt modifier
  • the graphene composite rubber asphalt modifier components are shown below (by parts by weight)
  • the specific surface area of the reduced graphene oxide is 400 m2 / g, and the powder particle size of the rubber powder is 40 mesh.
  • the preparation method of the graphene composite rubber asphalt modifier is as follows:
  • the graphene composite rubber asphalt modifier components are shown below (by parts by weight)
  • the specific surface area of the graphene microchip is 600 m2 / g, and the powder particle size of the rubber powder is 80 mesh.
  • the preparation method of the graphene composite rubber asphalt modifier is as follows:
  • the graphene microchips and the paraffinic rubber oil are mixed at a mass ratio of 0.005: 20, mechanically stirred, and dispersed at 120 ° C. for 50 minutes using a high-speed shearing machine, and cooled to obtain a graphene dispersion liquid.
  • Rubber powder 87 copies
  • the graphene composite rubber asphalt modifier in Example 1-3 and the non-graphene rubber asphalt modifier in Example 4 were used to modify the 70 # matrix asphalt, respectively.
  • the weight ratio of the graphene composite rubber asphalt modifier modifier to the matrix asphalt is 20:80
  • the weight ratio of the graphene-free rubber asphalt modifier to matrix asphalt according to Example 4 is 20:80.
  • the test uses relevant technology Standard specifications are carried out. Among them, the technical specifications of graphene rubber asphalt modifiers are shown in Table 1, and the specifications of graphene rubber asphalt mixtures (that is, after the modifier is added to the asphalt) are shown in Table 2.
  • the graphite thin composite rubber asphalt modifier in Examples 1-3 is higher than the graphene-free rubber asphalt modified in Example 4 in both the modified softening point and the 10 ° C ductility.

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Abstract

一种石墨烯复合橡胶沥青改性剂及其制备方法和应用，该石墨烯复合橡胶沥青改性剂包括以下重量份的组分：石墨烯粉体0.00005-0.01份，分散介质3-23份，橡胶粉78-92份，和添加剂0.05-6份；制备方法包括以下步骤：(1)将石墨烯粉体和分散介质进行混合，机械搅拌，进而通过高速分散后得到石墨烯分散液；和(2)将所述石墨烯分散液与橡胶粉和添加剂进行密炼，制成上述石墨烯复合橡胶沥青改性剂。

Description

石墨烯复合橡胶沥青改性剂及其制备方法和应用 技术领域
本发明是关于沥青改性剂领域，特别是关于一种石墨烯复合橡胶沥青改性剂及制备方法和应用。
背景技术
沥青路面具有行车舒适、安静、维修便捷等特点，目前全世界95％以上道路铺设的是沥青路面，沥青路面的重要材料组成从最初的渣油、经历了普通沥青、重交沥青到现今使用量超过50％的改性沥青，随着经济的高速发展交通荷载的快速增加，普通沥青或重交沥青修筑的沥青路面已出现各种问题，如高温性能不足会出现龟裂、车辙、变形，在低温性能不足导致路面开裂等诸多问题，已无法满足现实使用要求。橡胶沥青是由废旧轮胎加工而成橡胶粉粒，再按一定比例与基质沥青充分融合后形成的沥青胶结材料。废橡胶改性沥青混合料的高温稳定性、抗车辙性能和抗疲劳性能等同或稍优于SBS改性沥青，但更符合环保要求，已经越来越引起各界重视。然而在橡胶粉改性沥青的实际应用中，还存在一些技术问题亟待解决，橡胶和基质沥青的相容性不足，导致改性后沥青的储存稳定性不佳，加工过程需要高温、并且伴随而来的严重的气味与粉尘的二次污染等问题，进而影响橡胶沥青的大规模应用。
石墨烯是一种新型功能材料，其结构中的碳原子之间通过较强的σ键连接，使石墨烯片有极优异的力学性能。目前，制备二维石墨烯的方法可分为两种：一种是自上而下的方法，就是从比石墨烯更高结构的石墨或者碳纳米管分解得到石墨烯，如机械剥离法、插层剥离法、溶剂液相剥离法和氧化还原法等；另外一种是自下而上的方法，就是利用比石墨烯更低结构的碳源(甲烷、CO、酒精等小分子)通过CVD、电弧放电、溶剂热法等制备石墨烯。石墨烯的在具体应用中的性能与制备方法有着息息相关。
目前石墨烯沥青方面，大部分采用氧化石墨烯，将氧化石墨烯作为添加剂，SBS作为改性剂，与基质沥青，含硫促进剂进行混合，得到石墨烯改性沥青；或者是将基质沥青和改性剂混合，再加入羧基改性氧化石墨烯，得到基于羧基改性氧化石墨烯的聚乙烯改性沥青；另外，还有将氧化石墨烯与乙醇按一定比例超声分散，配制成氧化 石墨烯溶胶，与中温煤沥青均匀混合搅拌，直至沥青中的溶剂挥发完为止，即得到最终产品。现有技术表明：石墨烯的添加可以提高沥青的粘附性，力学性能，高低温稳定性，高温抗车辙性等。
但由于氧化石墨烯有亲水性，与沥青的相容性差，尽管对其进行官能化，氧化石墨烯仍为二维片层结构，要将其在沥青中直接充分分散，技术上具有一定的难度；现有技术中采用氮或硫掺杂的石墨烯来提高石墨烯和沥青的交联度，但含硫物质不够环保，施工中若有有害物质释放，会危害健康。
目前石墨烯沥青方面采用的工艺大致如下：将石墨烯进行功能化，再将石墨烯、沥青和改性剂进行混合共融，这种共融的混合方式，使三者的界面性能差，相容性不佳，导致石墨烯在沥青中的分散程度不高，稳定性无法得到保障。
因此，采用共融的混合方式使石墨烯在沥青中直接分散就需要比较高的添加量才能增强效果，在现有技术中，石墨烯添加量占沥青总质量的0.1％～5％之间，有的甚至高达10％以上。这就大大提高了石墨烯改性沥青的成本，不利于推广使用。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。
发明内容
本发明的目的在于提供一种石墨烯复合橡胶沥青改性剂及其制备方法和应用，该石墨烯复合橡胶沥青改性剂能够大幅提高橡胶粉在沥青中的相容性和稳定度，可提高改性沥青与砂石的粘结性能、高低温稳定性能，同时降低路面的温度和延长路面使用寿命。
为实现上述目的，本发明提供了一种石墨烯复合橡胶沥青改性剂，包括以下重量份的组分：石墨烯粉体0.00005-0.01份，分散介质3-23份，橡胶粉78-92份，和添加剂0.05-6份；优选的，所述石墨烯复合橡胶沥青改性剂包括以下重量份的组分：石墨烯粉体0.0001-0.005份，分散介质5-20份，橡胶粉80-90份，和添加剂0.1-5份；进一步优选的，所述石墨烯复合橡胶沥青改性剂包括以下重量份的组分：石墨烯粉体0.003份，分散介质13份，橡胶粉85份，和添加剂2.5份。
在一优选的实施方式中，所述石墨烯粉体选自石墨烯微片、还原氧化石墨烯和立体构造石墨烯中的至少一种；优选的，所述石墨烯粉体为立体构造石墨烯；进一步优选的，所述石墨烯粉体的比表面积≥300m2/g；其中，石墨烯微片(Graphene Nanoplatelets)是指碳 层数少于10层、横向维度在100纳米至1000微米范围内的超薄的石墨烯层状堆积体；还原氧化石墨烯是将石墨首先氧化为氧化石墨，再通过剥离作用转化为氧化石墨烯，最后可通过各种还原方法(得到电化学、光化学等性能优异的石墨烯；立体构造石墨烯是由二维石墨烯片构成的具有类蜂窝状结构的粉体材料，其结构基本特征符合技术标准DB 45/T 1421-2016和DB 45/T 1425-2016的要求。
在一优选的实施方式中，所述分散介质选自链烷烃橡胶油、芳香基橡胶油、环烷基橡胶油和多环芳香烃橡胶油中的至少一种；优选的，所述分散介质选自链烷烃橡胶油、芳香基橡胶油和环烷基橡胶油中的至少一种；进一步优选的，所述分散介质为环烷基橡胶油。
在一优选的实施方式中，所述橡胶粉的粉末粒度为20-200目；优选的，所述橡胶粉的粉末粒度为30-150目；进一步优选的，所述橡胶粉的粉末粒度为40-80目。
在一优选的实施方式中，所述添加剂选自丙烯腈-丁二烯-苯乙烯共聚物、聚乙烯、乙撑双硬脂酸酰胺，C9石油树脂、C12石油树脂、硅烷偶联剂KH-580、硅烷偶联剂KH550、硅烷偶联剂KH792、十二烷基三甲氧基硅烷、十六烷基三甲氧基硅烷、分散剂KC163、分散剂BYK110、分散剂BYK164中的至少一种；优选的，所述添加剂选自丙烯腈-丁二烯-苯乙烯共聚物、聚乙烯和乙撑双硬脂酸酰胺中的至少一种；进一步优选的，所述添加剂为丙烯腈-丁二烯-苯乙烯共聚物。此添加剂为增加石墨烯稀与橡胶粉的界面相互作用和稳定分散石墨烯的作用。
本发明还提供了一种石墨烯复合橡胶沥青改性剂的制备方法，包括以下步骤：(1)将石墨烯粉体和分散介质进行混合，机械搅拌，进而通过高速分散后得到石墨烯分散液；(2)将所述石墨烯分散液与橡胶粉和添加剂进行密炼，制成上述石墨烯复合橡胶沥青改性剂。
在一优选的实施方式中，步骤(1)中，所述石墨烯粉体与分散介质进行混合的质量比为(0.00005-0.01)：(3-23)；优选的，所述石墨烯粉体与分散介质进行混合的质量比为(0.0001-0.005)：(5-20)；进一步优选的，所述石墨烯粉体与分散介质进行混合的质量比为0.003：13。
在一优选的实施方式中，步骤(1)中，高速分散是通过高速剪切机在60-120℃条件下对石墨烯粉体和分散介质混合后的液体进行分散10-60min，冷却后得到石墨烯分散液，所述石墨烯分散液中石墨烯的片径分布为100-2000纳米；优选的，高速剪切机是在70℃条件下对石墨烯和分散介质混合后的液体进行分散20-50min；进一步优选的，高速剪切机是在70℃条件下对石墨烯粉体和分散介质混合后的液体进行分散35min；进一步优选的， 所述石墨烯分散液中石墨烯的片径分布为500-1000纳米。
在一优选的实施方式中，步骤(2)中，将石墨烯分散液、橡胶粉和添加剂以(3-23)：(78-92)：(0.05-6)的质量比在200～260℃进行密炼揉搓10-60min，冷却后，制成石墨烯复合橡胶沥青改性剂；优选的，步骤(2)中，将石墨烯分散液、橡胶粉和添加剂以(5-20)：(80-90)：(0.1-5)的质量比在220-240℃进行密炼揉搓20-50min；进一步优选的，步骤(2)中，将石墨烯分散液、橡胶粉和添加剂以13：85：2.5的质量比在230℃进行密炼揉搓35min。
本发明还提供了上述石墨烯复合橡胶沥青改性剂或其制备方法在沥青改性剂方面的应用。
与现有技术相比，本发明具有如下有益效果：
(1)本发明所涉及的石墨烯复合橡胶沥青改性剂选自石墨烯微片、还原氧化石墨烯和立体构造石墨烯中的至少一种，其分散性比氧化石墨烯好；
(2)本发明所涉及的石墨烯复合橡胶沥青改性剂的制备方法，采用高温密炼的工艺，使石墨烯与橡胶粉充分混合，提高石墨烯的改性效果，避免石墨烯直接和基质沥青混合造成分散不充分；
(3)本发明采用的石墨烯粉体和高温密炼工艺相结合，在沥青中使用0.01％以下的石墨烯粉体就能起到较好的效果，大大降低石墨烯改性沥青的成本，该石墨烯复合橡胶沥青改性剂可大幅提高橡胶粉在沥青中的相容性和稳定度，可提高改性沥青与砂石的粘结性能、高低温稳定性能，同时降低路面的温度和延长路面使用寿命。
具体实施方式
下面对本发明的具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。
除非另有其它明确表示，否则在整个说明书和权利要求书中，术语“包括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的元件或组成部分，而并未排除其它元件或其它组成部分。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径可购得。
实施例1石墨烯复合橡胶沥青改性剂的组分及制备方法
石墨烯复合橡胶沥青改性剂组分如下所示(按重量份计)
Figure PCTCN2019091060-appb-000001
上述立体构造石墨烯的比表面积为500m2/g，橡胶粉的粉末粒度为60目。
上述石墨烯复合橡胶沥青改性剂的制备方法如下：
(1)将立体构造石墨烯和环烷基橡胶油按质量比0.003：13混合，机械搅拌，90℃条件下，利用高速剪切机分散35分钟，冷却后得到石墨烯分散液；
(2)将上述制备的石墨烯分散液与橡胶粉和丙烯腈-丁二烯-苯乙烯共聚物按质量比13：85：2.5加入密炼机中，在230℃进行高温密炼揉搓35分钟，冷却后，制成石墨烯复合橡胶沥青改性剂。
实施例2石墨烯复合橡胶沥青改性剂的组分及制备方法
石墨烯复合橡胶沥青改性剂组分如下所示(按重量份计)
Figure PCTCN2019091060-appb-000002
上述还原氧化石墨烯的比表面积为400m2/g，橡胶粉的粉末粒度为40目。
上述石墨烯复合橡胶沥青改性剂的制备方法如下：
(1)将还原氧化石墨烯和芳香基橡胶油按质量比0.0001：5混合，机械搅拌，60℃条件下，利用高速剪切机分散20分钟，冷却后得到石墨烯分散液；
(2)将上述制备的石墨烯分散液与橡胶粉和聚乙烯按质量比5：80：0.1加入密炼机中，在220℃进行高温密炼揉搓20分钟，冷却后，制成石墨烯复合橡胶沥青改性剂。
实施例3石墨烯复合橡胶沥青改性剂的组分及制备方法
石墨烯复合橡胶沥青改性剂组分如下所示(按重量份计)
Figure PCTCN2019091060-appb-000003
Figure PCTCN2019091060-appb-000004
上述石墨烯微片的比表面积为600m2/g，橡胶粉的粉末粒度为80目。
上述石墨烯复合橡胶沥青改性剂的制备方法如下：
(1)将石墨烯微片和链烷烃橡胶油按质量比0.005：20混合，机械搅拌，120℃条件下，利用高速剪切机分散50分钟，冷却后得到石墨烯分散液。
(2)将上述制备的石墨烯分散液与橡胶粉和乙撑双硬脂酸酰胺按质量比20：90：5加入密炼机中，在240℃进行高温密炼揉搓50分钟，冷却后，制成石墨烯复合橡胶沥青改性剂。
实施例4无石墨烯橡胶沥青改性剂
无石墨烯橡胶沥青改性剂的组分如下所示(按重量份计)
环烷基橡胶油                    12份
橡胶粉                          87份
丙烯腈-丁二烯-苯乙烯共聚物      1份
除了没有添加石墨烯粉体以外，该无石墨烯橡胶沥青改性剂的制备方法同实施例1。
对比例
将实施例1-3中的石墨烯复合橡胶沥青改性剂与实施例4中的无石墨烯橡胶沥青改性剂分别对70#基质沥青进行改性，其中实施例1-3中所涉及的石墨烯复合橡胶沥青改性剂改性剂与基质沥青重量比均为20：80，实施例4所涉及的无石墨烯橡胶沥青改性剂与基质沥青重量比为20：80，测试采用相关技术标准规范进行，其中，石墨烯橡胶沥青改性剂产品技术指标详见表1，石墨烯橡胶沥青混合料(即将改性剂加入到沥青后)的指标详见表2。
表1产品技术指标
Figure PCTCN2019091060-appb-000005
Figure PCTCN2019091060-appb-000006
表2石墨烯橡胶沥青混合料(AC-16C)指标
Figure PCTCN2019091060-appb-000007
通过上述表1可得，实施例1-3中的石墨稀复合橡胶沥青改性剂无论在改性软化点还是在10℃延度方面均高于实施例4中的无石墨烯橡胶沥青改性剂，并且在将实施例1-4中所涉及的改性剂加入到沥青后，通过表2可得，在60℃、0.7Mpa动稳定度，浸水马歇尔残留稳定度，低温破坏弯拉强度以及劲度模量方面，混合有实施例1-3所涉及的石墨烯复合橡胶沥青改性剂的石墨烯橡胶沥青混合料要远超于混合有实施例4所涉及的无石墨烯橡胶沥青改性剂的石墨烯橡胶沥青混合料，从而，进一步印证了本发明所涉及的石墨烯复合橡胶沥青改性剂可大幅提高橡胶粉在沥青中的相容性和稳定度。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。

Claims (20)

  1. 一种石墨烯复合橡胶沥青改性剂，其特征在于，包括以下重量份的组分：石墨烯粉体0.00005-0.01份，分散介质3-23份，橡胶粉78-92份，和添加剂0.05-6份。
  2. 如权利要求1所述的石墨烯复合橡胶沥青改性剂，其特征在于，包括以下重量份的组分：石墨烯粉体0.0001-0.005份，分散介质5-20份，橡胶粉80-90份，和添加剂0.1-5份。
  3. 如权利要求1所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述石墨烯粉体选自石墨烯微片、还原氧化石墨烯和立体构造石墨烯中的至少一种。
  4. 如权利要求3所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述石墨烯粉体为立体构造石墨烯。
  5. 如权利要求1所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述石墨烯粉体的比表面积≥300m2/g。
  6. 如权利要求1所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述分散介质选自链烷烃橡胶油、芳香基橡胶油、环烷基橡胶油和多环芳香烃橡胶油中的至少一种。
  7. 如权利要求6所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述分散介质选自链烷烃橡胶油、芳香基橡胶油和环烷基橡胶油中的至少一种。
  8. 如权利要求1所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述橡胶粉的粉末粒度为20-200目。
  9. 如权利要求8所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述橡胶粉的粉末粒度为30-150目。
  10. 如权利要求1所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述添加剂选自丙烯腈-丁二烯-苯乙烯共聚物、聚乙烯、乙撑双硬脂酸酰胺，C9石油树脂、C12石油树脂、硅烷偶联剂KH-580、硅烷偶联剂KH550、硅烷偶联剂KH792、十二烷基 三甲氧基硅烷、十六烷基三甲氧基硅烷、分散剂KC163、分散剂BYK110、分散剂BYK164中的至少一种。
  11. 如权利要求10所述的石墨烯复合橡胶沥青改性剂，其特征在于，所述添加剂选自丙烯腈-丁二烯-苯乙烯共聚物、聚乙烯和乙撑双硬脂酸酰胺中的至少一种。
  12. 一种石墨烯复合橡胶沥青改性剂的制备方法，其特征在于，包括以下步骤：
    (1)将石墨烯粉体和分散介质进行混合，机械搅拌，进而通过高速分散后得到石墨烯分散液；
    (2)将所述石墨烯分散液与橡胶粉和添加剂进行密炼，制成权利要求1所述的石墨烯复合橡胶沥青改性剂。
  13. 如权利要求12所述的制备方法，其特征在于，步骤(1)中，所述石墨烯粉体与分散介质进行混合的质量比为(0.00005-0.01)：(3-23)。
  14. 如权利要求13所述的制备方法，其特征在于，步骤(1)中，所述石墨烯粉体与分散介质进行混合的质量比为(0.0001-0.005)：(5-20)。
  15. 如权利要求12所述的制备方法，其特征在于，步骤(1)中，高速分散是通过高速剪切机在60-120℃条件下对石墨烯粉体和分散介质混合后的液体进行分散10-60min，冷却后得到石墨烯分散液，所述石墨烯分散液中石墨烯的片径分布为100-2000纳米。
  16. 如权利要求15所述的制备方法，其特征在于，步骤(1)中，高速剪切机是在70℃条件下对石墨烯和分散介质混合后的液体进行分散20-50min。
  17. 如权利要求15所述的制备方法，其特征在于，步骤(1)中，所述石墨烯分散液中石墨烯的片径分布为500-1000纳米。
  18. 如权利要求12所述的制备方法，其特征在于，步骤(2)中，将石墨烯分散液、橡胶粉和添加剂以(3-23)：(78-92)：(0.05-6)的质量比在200～260℃进行密炼揉搓10-60min，冷却后，制成石墨烯复合橡胶沥青改性剂。
  19. 如权利要求18所述的制备方法，其特征在于，步骤(2)中，将石墨烯分散液、橡胶粉和添加剂以(5-20)：(80-90)：(0.1-5)的质量比在220-240℃进行密炼揉搓20-50min。
  20. 权利要求1-11任一项所述的石墨烯复合橡胶沥青改性剂或权利要求12-19任一项所述的制备方法在沥青改性剂方面的应用。
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