WO2019223201A1 - Biological epoxy asphalt and preparation method therefor and application thereof - Google Patents
Biological epoxy asphalt and preparation method therefor and application thereof Download PDFInfo
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- WO2019223201A1 WO2019223201A1 PCT/CN2018/106861 CN2018106861W WO2019223201A1 WO 2019223201 A1 WO2019223201 A1 WO 2019223201A1 CN 2018106861 W CN2018106861 W CN 2018106861W WO 2019223201 A1 WO2019223201 A1 WO 2019223201A1
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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
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/26—Bituminous materials, e.g. tar, pitch
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Definitions
- the invention belongs to the field of construction, and particularly relates to a biological epoxy asphalt and a preparation method and application thereof.
- epoxy asphalt and bio-asphalt often faces the following problems: the high cost of petroleum epoxy resin and curing agent, the brittleness of epoxy resin after curing reaction, and the patented product properties of existing epoxy asphalt on the market
- epoxy asphalt is only used in special pavement structures such as long-span steel bridge decks and airport runways, which limits its use in road pavements.
- the bio-asphalt has a higher content of light components due to the rapid heating and rapid cooling manufacturing process in high-temperature cracking, and the raw material biomass generally contains higher oxygen elements, which leads to the oxygen content in the finished product (> 15 %) Is much higher than the content of oxygen in petroleum asphalt ( ⁇ 1%).
- a biological epoxy asphalt including three components A, B and C, component A includes epoxy soybean oil and diluent, component B includes curing agent, accelerator and defoamer, and component C includes asphalt;
- the mass ratio of the A component and the B component is 105 to 126: 45, and the ratio of the sum of the masses of the A component and the B component to the mass of the C component is 100: 57 to 520;
- the diluent is an epoxy resin reactive diluent, preferably phenyl glycidyl ether or benzyl glycidyl ether.
- the curing agent is a long-chain aliphatic primary amine, preferably octadecyl primary amine or tallow amine.
- the defoamer is a low-molecular-weight polyether having a molecular weight of 2000 or less, preferably a copolymer of ethylene oxide and propylene oxide.
- the asphalt is road petroleum asphalt No. 70 or road petroleum asphalt No. 90.
- component A After mixing the formulated amounts of epoxy soybean oil and diluent, heat to 160 ⁇ 2 °C, stir for 100 ⁇ 140min, and then cool for 23 ⁇ 25h at room temperature to obtain the biological ring.
- a component of oxygen pitch After mixing the formulated amounts of epoxy soybean oil and diluent, heat to 160 ⁇ 2 °C, stir for 100 ⁇ 140min, and then cool for 23 ⁇ 25h at room temperature to obtain the biological ring.
- component B After mixing the formulating amount of curing agent, accelerator and defoaming agent uniformly, heating to 98-102 ° C, fully reacting for 27-33min, and then cooling to room temperature to obtain biological epoxy Asphalt B component;
- the present invention has the following advantages:
- the construction time of warm-mixed epoxy asphalt can't exceed 90min at the longest, and the construction time of hot-mixed epoxy asphalt can be 30 ⁇ 120min technology ", author: Zhou Jinxia), by contrast, shelter construction time biological epoxy asphalt up to 3h, from mixing, transportation, rolling to complete the paving has longer operating time, effectively ensuring the road Construction Quality;
- the production process of epoxy soybean oil has the characteristics of bio-renewable, environmental protection, and cheap, which greatly reduces the energy consumption during the production of epoxy asphalt. As a pavement layer of transportation infrastructure, it is more green, environmentally friendly and consistent with sustainable development idea.
- Example 1 Weigh 100 parts of epoxy soybean oil, add 20 parts of phenyl glycidyl ether, start stirring, gradually heat up to 160 ° C, and cool to room temperature after 2 hours of reaction to obtain component A of the biological epoxy material.
- Example 2 Weigh 100 parts of epoxy soybean oil, add 20 parts of benzyl glycidyl ether, start stirring, gradually heat up to 160 ° C., and cool to room temperature after 2 hours of reaction to obtain component A of the biological epoxy material.
- Example 3 Weigh 100 parts of epoxy soybean oil, add 30 parts of benzyl glycidyl ether, start stirring, gradually heat up to 160 ° C, and cool to room temperature after 2 hours of reaction to obtain the A component of the biological epoxy material.
- the preparation method of the component B of the epoxy epoxy asphalt is as follows:
- Example 4 Weigh 45 parts of octadecyl primary amine, 1 part of aromatic amine, 1 part of low molecular weight polyether, heat to 100 ° C, mechanically stir for 30 min, and cool to room temperature to obtain the B component of biological epoxy asphalt .
- Example 6 110 parts of the A component of the bio-epoxy asphalt material obtained in Example 1 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 4 were heated to 60 ° C. respectively, and then Group A Slowly pour component B, mix and stir at 2000 r / min using a high-speed stirring and shearing device for 3 minutes. Pour the mixture into 150 parts of component C (asphalt 70) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material. The cured bio-epoxy asphalt material was punched into tensile test strips for mechanical property testing. The test temperature was 23 ° C and the tensile speed was 500 mm / min. The above test results are shown in Schedule 1.
- Example 7 120 parts of the A component of the bio-epoxy asphalt material obtained in Example 2 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 5 were heated to 60 ° C. respectively, and then Group A Slowly pour component B, and use a high-speed stirring and shearing device to mix and stir at a speed of 2000 r / min for 3 minutes. Pour the mixture of the two into 300 parts of component C (asphalt 70) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material.
- the tensile test conditions are the same as in Example 6. The test results are shown in Table 1.
- Example 9 Six parts of the epoxy asphalt mixture obtained in Example 6 and 94 parts of a certain gradation aggregate were heated to 150 ° C. The gradation of the aggregate is shown in Table 2 and mixed for 1 min. After the actual forming, curing was performed at 60 ° C for 3 days to obtain a high-performance epoxy asphalt mixture. The obtained epoxy asphalt mixture was subjected to a Marshall test, a -15 ° C low-temperature bending test, and a rutting test. The results of the above tests are shown in Table 3.
- Example 10 Example 11 Marshall stability / kN JTG E20-2011 93 89 86 Current value / 0.1mm JTG E20-2011 31 33 36 Void ratio /% JTG E20-2011 1.8 1.9 1.8 Bending stiffness modulus / Mpa JTG E20-2011 14032 13542 13028 Bending strain / 10 -3 JTG E20-2011 3.21 3.12 3.01 Dynamic stability / times / mm JTG E20-2011 24532 24512 22318
- the preparation method is the same as that in Example 6, except that the A component of the bio-epoxy asphalt material is obtained by the following method: 100 parts of epoxy soybean oil is weighed, 20 parts of phenyl glycidyl ether is added, stirring is started, and heating is gradually performed The temperature was raised to 110-120 ° C, and the reaction was cooled to room temperature after 2 hours to obtain the A component of the biological epoxy material.
- the obtained bio-epoxy asphalt material was reference product 1.
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Abstract
Disclosed by the present invention is a biological epoxy asphalt, comprising a component A, a component B and a component C. The component A includes epoxidized soybean oil and a diluent, the component B includes a curing agent, an accelerant and a defoaming agent, and the component C includes asphalt. The mass ratio of the component A to the component B is (105~126) : 45, and the mass ratio of the sum of the component A and the component B to the component C is 100 : (57~520). Compared with the prior art, the biological epoxy asphalt disclosed by the present invention can be used to replace the traditional petroleum asphalt; by utilizing the materials such as epoxidized soybean oil and biological curing agent, the cost is remarkably lowered, and the thermoplastic property of the traditional asphalt material can be effectively improved, so that the biological epoxy asphalt has excellent high-and-low temperature performance and anti-aging property and can be widely applied to the pavements of highways, tunnels and the like and bridge deck pavement. Further disclosed by the present invention is a preparation method for the biological epoxy asphalt.
Description
本发明属于建筑领域，具体涉及一种生物环氧沥青及其制备方法与应用。The invention belongs to the field of construction, and particularly relates to a biological epoxy asphalt and a preparation method and application thereof.
环氧沥青是一种由环氧树脂、固化剂、石油沥青发生不可逆化学交联固化反应而形成的三维连续相的热固性材料。随着温度升高，环氧沥青不会像传统沥青一样软化，具有良好的耐老化和抗化学腐蚀性，环氧沥青混凝土的疲劳性能比Superpave聚合物改性沥青混凝土大三个数量级，能够很好的适用于重载大交通量和宽域气温的作用，大大提升路用性能。另一方面，生物沥青作为传统石油沥青的一种可替代产品，可取材于多种生物质材料，如麦秸秆、废木屑、地沟油等，一定程度上可以“变废为宝”，作为石油沥青的有效补充并对石油沥青进行性能方面的改性。加之，人们对环境、气候、不可再生资源枯竭等问题的日益关注，因此采用生物材料替代石油材料以实现交通基础设施的可持续性发展已经成为全球交通基础设施技术研究的前沿热点。Epoxy pitch is a three-dimensional continuous phase thermosetting material formed by irreversible chemical cross-linking curing reaction of epoxy resin, curing agent and petroleum pitch. As the temperature rises, epoxy asphalt will not soften like traditional asphalt, and has good aging resistance and chemical resistance. The fatigue performance of epoxy asphalt concrete is three orders of magnitude greater than that of Superpave polymer modified asphalt concrete. Good for heavy traffic and wide area air temperature, greatly improving road performance. On the other hand, bio-asphalt, as an alternative product of traditional petroleum pitch, can be obtained from a variety of biomass materials, such as wheat straw, waste wood chips, trench oil, etc., to a certain extent, it can be "turned into treasure" as petroleum. Effective addition of asphalt and performance modification of petroleum asphalt. In addition, people are paying more and more attention to the environment, climate, and the depletion of non-renewable resources. Therefore, the use of biomaterials to replace petroleum materials to achieve sustainable development of transportation infrastructure has become the hotspot of global transportation infrastructure technology research.
而目前环氧沥青与生物沥青的应用过程中常常面临着以下问题：石油环氧树脂和固化剂的高成本、固化反应后环氧树脂的脆性以及市场上现有的环氧沥青的专利产品属性，使得环氧沥青仅应用于大跨钢桥面铺装、机场跑道等特殊路面结构中，限制了其在道路路面中的使用。而生物沥青因为高温裂解中快速升温和快速冷却的制造工艺使其含有较高的轻质组分含量，以及原材料生物质中一般含有较高的氧元素，导致其成品中氧元素含量(>15％)远高于石油沥青中氧元素含量(<1％)。在高温施工过程中，轻质组分易于析出，从而导致剩余的沥青混合料力学性能下降；同时，生物沥青中很多化学成分在高温下易于氧化，而使生物沥青总体表现为快速硬化，路面使用性能下降。At present, the application of epoxy asphalt and bio-asphalt often faces the following problems: the high cost of petroleum epoxy resin and curing agent, the brittleness of epoxy resin after curing reaction, and the patented product properties of existing epoxy asphalt on the market As a result, epoxy asphalt is only used in special pavement structures such as long-span steel bridge decks and airport runways, which limits its use in road pavements. The bio-asphalt has a higher content of light components due to the rapid heating and rapid cooling manufacturing process in high-temperature cracking, and the raw material biomass generally contains higher oxygen elements, which leads to the oxygen content in the finished product (> 15 %) Is much higher than the content of oxygen in petroleum asphalt (<1%). During high-temperature construction, light components are liable to precipitate, which causes the mechanical properties of the remaining asphalt mixture to decrease. At the same time, many chemical components in the bio-asphalt are susceptible to oxidation at high temperatures, which makes the bio-asphalt appear to be rapidly hardened. Degraded performance.
发明内容Summary of the Invention
本发明要解决的技术问题是提供一种生物环氧沥青，以解决现有技术存在的效果不佳等问题。The technical problem to be solved by the present invention is to provide a biological epoxy asphalt to solve the problems such as poor effect existing in the prior art.
为解决上述技术问题，本发明采用的技术方案如下：To solve the above technical problems, the technical solutions adopted by the present invention are as follows:
一种生物环氧沥青，包括A、B和C三个组分，A组分包括环氧大豆油和稀释剂，B组分包括固化剂、促进剂和消泡剂，C组分包括沥青；A biological epoxy asphalt, including three components A, B and C, component A includes epoxy soybean oil and diluent, component B includes curing agent, accelerator and defoamer, and component C includes asphalt;
其中，A组分与B组分的质量比为105～126：45，A组分和B组分的质量之和与C 组分的质量的比为100：57～520；Among them, the mass ratio of the A component and the B component is 105 to 126: 45, and the ratio of the sum of the masses of the A component and the B component to the mass of the C component is 100: 57 to 520;
其中，A组分中，环氧大豆油和稀释剂的质量比为100：10～30；B组分中，固化剂、促进剂和消泡剂的质量比为45：0.5～1：0.6～1。Among them, in the component A, the mass ratio of the epoxy soybean oil and the diluent is 100: 10 to 30; in the component B, the mass ratio of the curing agent, the accelerator and the defoaming agent is 45: 0.5 to 1: 0.6 to 1.
其中，所述的稀释剂为环氧树脂活性稀释剂，优选苯基缩水甘油醚或苯甲醇缩水甘油醚。Wherein, the diluent is an epoxy resin reactive diluent, preferably phenyl glycidyl ether or benzyl glycidyl ether.
其中，所述的固化剂为长链脂肪族伯胺，优选十八烷基伯胺或牛脂胺。Wherein, the curing agent is a long-chain aliphatic primary amine, preferably octadecyl primary amine or tallow amine.
其中，所述的促进剂为芳香胺或碱；其中，所述的芳香胺为苄胺，所述的碱为强碱，优选氢氧化钾。The promoter is an aromatic amine or a base; wherein the aromatic amine is a benzylamine and the base is a strong base, preferably potassium hydroxide.
其中，所述的消泡剂为分子量在2000以下的低分子量聚醚，优选环氧乙烷和环氧丙烷的共聚物。The defoamer is a low-molecular-weight polyether having a molecular weight of 2000 or less, preferably a copolymer of ethylene oxide and propylene oxide.
其中，所述的沥青为70号道路石油沥青或90号道路石油沥青。Wherein, the asphalt is road petroleum asphalt No. 70 or road petroleum asphalt No. 90.
上述生物环氧沥青的制备方法，它包括如下步骤：The method for preparing the above-mentioned bio-epoxy asphalt includes the following steps:
(1)A组分的制备：将配方量的环氧大豆油和稀释剂混合均匀后，加热至160±2℃，搅拌反应100～140min后，在室温下冷却23～25h，即得生物环氧沥青A组分；(1) Preparation of component A: After mixing the formulated amounts of epoxy soybean oil and diluent, heat to 160 ± 2 ℃, stir for 100 ～ 140min, and then cool for 23 ～ 25h at room temperature to obtain the biological ring. A component of oxygen pitch;
(2)B组分的制备：将配方量的固化剂、促进剂和消泡剂混合均匀后，加热至98～102℃后，充分反应27～33min后再冷却至室温，即得生物环氧沥青B组分；(2) Preparation of component B: After mixing the formulating amount of curing agent, accelerator and defoaming agent uniformly, heating to 98-102 ° C, fully reacting for 27-33min, and then cooling to room temperature to obtain biological epoxy Asphalt B component;
(3)将加热至58～62℃的步骤(1)中制备得到的A组分倒入加热至58～62℃的步骤(2)中制备得到的B组分中，采用高速搅拌剪切设备以2000±200r/min的转速进行混合搅拌2～3min，混合均匀后倒入加热至148～152℃的C组分中，继续采用高速搅拌剪切设备以2000±200r/min的转速混合搅拌1～2min，混合均匀后经固化得到生物环氧沥青。(3) Pour component A prepared in step (1) heated to 58-62 ° C into component B prepared in step (2) heated to 58-62 ° C, and use high-speed stirring and shearing equipment Mix and stir at a speed of 2000 ± 200r / min for 2 ~ 3min, mix well and pour into component C heated to 148 ～ 152 ℃, continue to use a high-speed stirring shearing device to mix and stir at a speed of 2000 ± 200r / min ～ 2min. After mixing evenly, the epoxy epoxy pitch is obtained after curing.
步骤(3)中，所述的固化为60±2℃下固化70～74h。In step (3), the curing is performed at 60 ± 2 ° C for 70-74 hours.
上述生物环氧沥青在制备环氧沥青混合料中的应用也在本发明的保护范围之内。The application of the above-mentioned biological epoxy asphalt in preparing epoxy asphalt mixture is also within the protection scope of the present invention.
其中，所述的应用方法为：将按照级配要求配好的集料与矿粉在150±2°℃下保温4h，同时将上述制备得到的生物环氧沥青材料加热至150±2℃，取出集料倒入150±2℃的拌合锅中拌合30±2s，而后将生物环氧沥青材料和矿粉同时倒入拌合锅中以50±5r/min的转速进行拌合2～3min，直至沥青混合料拌合均匀无花白料，得到高性能生物环氧沥青混合料。Wherein, the application method is as follows: the aggregate and mineral powder prepared according to the grading requirements are kept at 150 ± 2 ° C for 4 hours, and the bio-epoxy asphalt material prepared above is heated to 150 ± 2 ° C, Take out the aggregate and pour it into a mixing pot at 150 ± 2 ℃ and mix for 30 ± 2s, then pour the bio-epoxy asphalt material and mineral powder into the mixing pot at the same time and mix at a speed of 50 ± 5r / min. 2 ～ 3 minutes, until the asphalt mixture is mixed uniformly with no white matter, to obtain a high-performance biological epoxy asphalt mixture.
与现有技术相比，本发明具有如下优势：Compared with the prior art, the present invention has the following advantages:
1.本发明使用环氧大豆油代替传统环氧树脂制备得到的生物环氧沥青，能够有效减缓生物沥青的老化现象，减少生物油轻组分的析出和氧化，一定程度上突破了生物沥青于交通基础设施行业内应用的壁垒；1. The present invention uses epoxy soybean oil instead of traditional epoxy resin to prepare bio-epoxy pitch, which can effectively slow the aging phenomenon of bio-asphalt, reduce the precipitation and oxidation of light components of bio-oil, and to a certain extent break through bio-asphalt in Barriers applied in the transportation infrastructure industry;
2.当前市场上传统环氧树脂的价格约为27000元/吨，环氧大豆油的价格约为7000元/吨，使用环氧大豆油代替传统的环氧树脂，能够有效降低环氧沥青混合料的材料成本，有利于环氧沥青在道路工程中的推广使用；2. The current price of traditional epoxy resin in the market is about 27,000 yuan / ton, and the price of epoxy soybean oil is about 7,000 yuan / ton. Using epoxy soybean oil instead of traditional epoxy resin can effectively reduce the epoxy asphalt mixture. Material cost of materials is beneficial to the popularization and use of epoxy asphalt in road engineering;
3.相比于传统的石油沥青，生物环氧沥青使从根本上改变了其低温脆、高温软的热塑性性质，具有优异的高低温和抗老化特性，较好地满足了路面以及桥梁铺装中的使用需求；3. Compared with traditional petroleum asphalt, bio-epoxy asphalt fundamentally changes its low-temperature brittle, high-temperature soft thermoplastic properties, has excellent high-low temperature and anti-aging characteristics, and satisfies the road and bridge paving requirements. Demand for use
4.温拌环氧沥青的可施工时间最长不超过90min，热拌环氧沥青的可施工时间为30～120min(见现有文献“南京铁心桥钢桥面热拌环氧沥青混凝土铺装技术”，作者：周金霞)，相比之下，生物环氧沥青的施工容留时间长达3h，从拌合、运输、摊铺至碾压完成具有更久的操作时间，有效保证了路面的施工质量；4. The construction time of warm-mixed epoxy asphalt can't exceed 90min at the longest, and the construction time of hot-mixed epoxy asphalt can be 30 ～ 120min technology ", author: Zhou Jinxia), by contrast, shelter construction time biological epoxy asphalt up to 3h, from mixing, transportation, rolling to complete the paving has longer operating time, effectively ensuring the road Construction Quality;
5.环氧大豆油的生产过程具有生物可再生、环保、廉价等特点，大大降低了环氧沥青生产过程中的能量消耗，作为交通基础设施的铺装层更加绿色、环保，符合可持续发展理念。5. The production process of epoxy soybean oil has the characteristics of bio-renewable, environmental protection, and cheap, which greatly reduces the energy consumption during the production of epoxy asphalt. As a pavement layer of transportation infrastructure, it is more green, environmentally friendly and consistent with sustainable development idea.
根据下述实施例，可以更好地理解本发明。然而，本领域的技术人员容易理解，实施例所描述的内容仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。The invention can be better understood from the following examples. However, those skilled in the art can easily understand that the content described in the embodiments is only used to illustrate the present invention, and should not and should not limit the present invention described in detail in the claims.
下面通过实例详述本发明，在以下实施例中，各组分的份数均为质量份数。The present invention is described in detail below by examples. In the following examples, the parts of each component are all parts by mass.
生物环氧沥青A组分制备方法如下：The preparation method of the biological epoxy asphalt A component is as follows:
实施例1：称取100份环氧大豆油，加入20份苯基缩水甘油醚，开始搅拌，逐渐加热升温至160℃，反应2h后冷却至室温，得到生物环氧材料的A组分。Example 1: Weigh 100 parts of epoxy soybean oil, add 20 parts of phenyl glycidyl ether, start stirring, gradually heat up to 160 ° C, and cool to room temperature after 2 hours of reaction to obtain component A of the biological epoxy material.
实施例2：称取100份环氧大豆油，加入20份苯甲醇缩水甘油醚，开始搅拌，逐渐加热升温至160℃，反应2h后冷却至室温，得到生物环氧材料的A组分。Example 2: Weigh 100 parts of epoxy soybean oil, add 20 parts of benzyl glycidyl ether, start stirring, gradually heat up to 160 ° C., and cool to room temperature after 2 hours of reaction to obtain component A of the biological epoxy material.
实施例3：称取100份环氧大豆油，加入30份苯甲醇缩水甘油醚，开始搅拌，逐渐 加热升温至160℃，反应2h后冷却至室温，得到生物环氧材料的A组分。Example 3: Weigh 100 parts of epoxy soybean oil, add 30 parts of benzyl glycidyl ether, start stirring, gradually heat up to 160 ° C, and cool to room temperature after 2 hours of reaction to obtain the A component of the biological epoxy material.
生物环氧沥青B组分制备方法如下：The preparation method of the component B of the epoxy epoxy asphalt is as follows:
实施例4：分别称取45份十八烷基伯胺，1份芳香胺，1份低分子量聚醚，加热到100℃，机械搅拌30min后冷却至室温，得到生物环氧沥青的B组分。Example 4: Weigh 45 parts of octadecyl primary amine, 1 part of aromatic amine, 1 part of low molecular weight polyether, heat to 100 ° C, mechanically stir for 30 min, and cool to room temperature to obtain the B component of biological epoxy asphalt .
实施例5：分别称取45份牛脂胺，1份KOH，1份低分子量聚醚，加热到100℃，机械搅拌30min后冷却至室温，得到生物环氧沥青的B组分。Example 5: Weigh 45 parts of tallow amine, 1 part of KOH, and 1 part of low molecular weight polyether, heat to 100 ° C, mechanically stir for 30 minutes, and then cool to room temperature to obtain the B component of biological epoxy asphalt.
下面给出本发明提供的生物环氧沥青A组分、B组分和C组分制备得到生物环氧沥青材料的实施例和测试结果：The following are examples and test results of the preparation of the biological epoxy asphalt material A, B and C components of the biological epoxy asphalt provided by the present invention:
实施例6：将110份实施例1中得到的生物环氧沥青材料的A组分和45份实施例4中得到的生物环氧沥青材料的B组分分别加热到60℃，然后将A组分缓慢倒入B组分，采用高速搅拌剪切设备以2000r/min的转速进行混合搅拌，搅拌时间为3min，将二者的混合物倒入150份150℃的C组分(70号沥青)中，继续采用高速搅拌剪切设备以2000r/min的转速进行混合搅拌，搅拌1min，60℃固化3d，得到生物环氧沥青材料。将固化后的生物环氧沥青材料冲裁成拉伸试样条做力学性能测试，试验温度为23℃，拉伸速度为500mm/min。上述测试结果见附表1。Example 6: 110 parts of the A component of the bio-epoxy asphalt material obtained in Example 1 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 4 were heated to 60 ° C. respectively, and then Group A Slowly pour component B, mix and stir at 2000 r / min using a high-speed stirring and shearing device for 3 minutes. Pour the mixture into 150 parts of component C (asphalt 70) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material. The cured bio-epoxy asphalt material was punched into tensile test strips for mechanical property testing. The test temperature was 23 ° C and the tensile speed was 500 mm / min. The above test results are shown in Schedule 1.
实施例7：将120份实施例2中得到的生物环氧沥青材料的A组分和45份实施例5中得到的生物环氧沥青材料的B组分分别加热到60℃，然后将A组分缓慢倒入B组分，采用高速搅拌剪切设备以2000r/min的转速进行混合搅拌，搅拌时间为3min，将二者的混合物倒入300份150℃的C组分(70号沥青)中，继续采用高速搅拌剪切设备以2000r/min的转速进行混合搅拌，搅拌1min，60℃固化3d，得到生物环氧沥青材料。拉伸试验条件同实施例6，测试结果见附表1。Example 7: 120 parts of the A component of the bio-epoxy asphalt material obtained in Example 2 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 5 were heated to 60 ° C. respectively, and then Group A Slowly pour component B, and use a high-speed stirring and shearing device to mix and stir at a speed of 2000 r / min for 3 minutes. Pour the mixture of the two into 300 parts of component C (asphalt 70) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material. The tensile test conditions are the same as in Example 6. The test results are shown in Table 1.
实施例8：将130份实施例1中得到的生物环氧沥青材料的A组分和45份实施例5中得到的生物环氧沥青材料的B组分分别加热到60℃，然后将A组分缓慢倒入B组分，采用高速搅拌剪切设备以2000r/min的转速进行混合搅拌，搅拌时间为3min，将二者的混合物倒入300份150℃的C组分(90号沥青)中，继续采用高速搅拌剪切设备以2000r/min的转速进行混合搅拌，搅拌1min，60℃固化3d，得到生物环氧沥青材料。拉伸试验条件同实施例6，测试结果见附表1。Example 8: 130 parts of the A component of the bio-epoxy asphalt material obtained in Example 1 and 45 parts of the B component of the bio-epoxy asphalt material obtained in Example 5 were heated to 60 ° C. respectively, and then Group A Slowly pour into component B, and use a high-speed stirring and shearing device to mix and stir at a speed of 2000 r / min for 3 minutes. Pour the mixture of the two into 300 parts of component C (90 pitch) at 150 ° C. Continue to use a high-speed stirring and shearing device to perform mixing and stirring at a speed of 2000 r / min, stir for 1 minute, and cure at 60 ° C for 3 days to obtain a biological epoxy asphalt material. The tensile test conditions are the same as in Example 6. The test results are shown in Table 1.
表1生物环氧沥青材料的力学性能Table 1 Mechanical properties of bio-epoxy asphalt materials
下面给出以本发明提供的生物环氧沥青A组分、B组分、C组分和适量集料、矿粉制备得到的生物环氧沥青的实施例和测试结果：Examples and test results of the bio-epoxy asphalt prepared by using the bio-epoxy asphalt A component, B-component, C-component, and appropriate amount of aggregate and mineral powder are provided below:
实施例9：将6份实施例6中得到环氧沥青混合物和94份一定级配的集料加热到150℃，其中集料的级配见附表2，拌合1min，采用轮碾法压实成型后，60℃养护3d，得到高性能环氧沥青混合料。将得到的环氧沥青混合料进行马歇尔试验、-15℃低温弯曲试验、车辙试验，上述测试结果见附表3。Example 9: Six parts of the epoxy asphalt mixture obtained in Example 6 and 94 parts of a certain gradation aggregate were heated to 150 ° C. The gradation of the aggregate is shown in Table 2 and mixed for 1 min. After the actual forming, curing was performed at 60 ° C for 3 days to obtain a high-performance epoxy asphalt mixture. The obtained epoxy asphalt mixture was subjected to a Marshall test, a -15 ° C low-temperature bending test, and a rutting test. The results of the above tests are shown in Table 3.
实施例10：将6.5份实施例7中得到环氧沥青混合物和93.5份一定级配的集料加热到150℃，其中集料的级配见附表2，拌合1min，采用轮碾法压实成型后，60℃养护3d，得到高性能环氧沥青混合料。路用性能试验同实例9，试验结果见附表3。Example 10: 6.5 parts of the epoxy asphalt mixture obtained in Example 7 and 93.5 parts of a certain gradation aggregate were heated to 150 ° C. The gradation of the aggregate is shown in Table 2 and mixed for 1 min. After the actual forming, curing was performed at 60 ° C for 3 days to obtain a high-performance epoxy asphalt mixture. The road performance test is the same as that in Example 9. The test results are shown in Table 3.
实施例11：将7份实施例8中得到的环氧沥青混合物和93份一定级配的集料加热到150℃，其中集料的级配见附表2，拌合1min，采用轮碾法压实成型后，60℃养护3d，得到高性能环氧沥青混合料。路用性能试验同实例9，试验结果见附表3。Example 11: Heat 7 parts of the epoxy asphalt mixture obtained in Example 8 and 93 parts of a certain gradation aggregate to 150 ° C. The gradation of the aggregate is shown in Table 2 and mixed for 1 min. After compaction and molding, curing was performed at 60 ° C for 3 days to obtain a high-performance epoxy asphalt mixture. The road performance test is the same as that in Example 9. The test results are shown in Table 3.
表2集料级配Table 2 Aggregate grading
| 筛孔尺寸(mm)Sieve hole size (mm) | 13.213.2 | 9.59.5 | 4.754.75 | 2.362.36 | 1.181.18 | 0.60.6 | 0.30.3 | 0.150.15 | 0.0750.075 |
| 通过百分率(％)Pass percentage (%) | 100100 | 97.297.2 | 32.432.4 | 27.327.3 | 19.519.5 | 13.513.5 | 9.99.9 | 8.28.2 | 6.56.5 |
表3生物环氧沥青混合料的性能Table 3 Performance of biological epoxy asphalt mixture
| 试验项目Pilot projects | 试验方法experiment method | 实施例9Example 9 | 实施例10Example 10 | 实施例11Example 11 |
| 马歇尔稳定度/kNMarshall stability / kN | JTG E20-2011JTG E20-2011 | 9393 | 8989 | 8686 |
| 流值/0.1mmCurrent value / 0.1mm | JTG E20-2011JTG E20-2011 | 3131 | 3333 | 3636 |
| 空隙率/％Void ratio /% | JTG E20-2011JTG E20-2011 | 1.81.8 | 1.91.9 | 1.81.8 |
| 弯曲劲度模量/MpaBending stiffness modulus / Mpa | JTG E20-2011JTG E20-2011 | 1403214032 | 1354213542 | 1302813028 |
| 弯曲应变/10 -3 Bending strain / 10 -3 | JTG E20-2011JTG E20-2011 | 3.213.21 | 3.123.12 | 3.013.01 |
| 动稳定度/次/mmDynamic stability / times / mm | JTG E20-2011JTG E20-2011 | 2453224532 | 2451224512 | 2231822318 |
实施例12：采用实施例9中制备得到的生物环氧沥青混合料进行实际路面的铺筑， 试验路段长300m，宽4m，上面层厚度为4cm。计算可得所需环氧大豆油的质量为2.54t，其材料成本为1.778万元。如若采用同等条件下的环氧树脂作为原材料，则所需材料成本为6.858万元。因此可以看出，仅仅铺筑300m长度的试验段就可以节省材料成本将近5.08万元，经济效益显著。Example 12: The bio-epoxy asphalt mixture prepared in Example 9 was used for paving the actual road surface. The length of the test section was 300m, the width was 4m, and the thickness of the upper layer was 4cm. According to the calculation, the required mass of epoxy soybean oil is 2.54t, and the material cost is 177.8 thousand yuan. If the epoxy resin under the same conditions is used as the raw material, the required material cost is 68.58 million yuan. Therefore, it can be seen that the cost of materials can be reduced by nearly 50,800 yuan only by laying a test section of 300m in length, and the economic benefits are significant.
对比例1：Comparative Example 1:
制备方法与实施例6相同，所不同的是，生物环氧沥青材料的A组分由如下方法得到：称取100份环氧大豆油，加入20份苯基缩水甘油醚，开始搅拌，逐渐加热升温至110～120℃，反应2h后冷却至室温，得到生物环氧材料的A组分。所得生物环氧沥青材料为对照品1。The preparation method is the same as that in Example 6, except that the A component of the bio-epoxy asphalt material is obtained by the following method: 100 parts of epoxy soybean oil is weighed, 20 parts of phenyl glycidyl ether is added, stirring is started, and heating is gradually performed The temperature was raised to 110-120 ° C, and the reaction was cooled to room temperature after 2 hours to obtain the A component of the biological epoxy material. The obtained bio-epoxy asphalt material was reference product 1.
对比例2：Comparative Example 2:
制备方法与实施例6相同，所不同的是，生物环氧沥青材料的A组分由如下方法得到：称取100份环氧大豆油，加入20份苯基缩水甘油醚，开始搅拌，逐渐加热升温至170～190℃，反应2h后冷却至室温，得到生物环氧材料的A组分。所得生物环氧沥青材料为对照品2。The preparation method is the same as that in Example 6, except that the A component of the bio-epoxy asphalt material is obtained by the following method: 100 parts of epoxy soybean oil is weighed, 20 parts of phenyl glycidyl ether is added, stirring is started, and heating is gradually performed The temperature was raised to 170-190 ° C, and the reaction was cooled to room temperature after 2 hours to obtain the A component of the biological epoxy material. The obtained bio-epoxy asphalt material was reference product 2.
将实施例6中的产品和对照品1以及对照品2的性能对比如下：The performance comparison between the product in Example 6 and Control 1 and Control 2 is as follows:
表4生物环氧沥青材料的力学性能Table 4 Mechanical properties of bio-epoxy asphalt materials
| 对比例Comparative example | 拉伸强度(MPa，23℃)Tensile strength (MPa, 23 ℃) | 断裂伸长率(％，23℃)Elongation at break (%, 23 ° C) |
| 44 | 1.751.75 | 8282 |
| 55 | 3.23.2 | 146146 |
| 66 | 5.845.84 | 352352 |
| 技术要求skills requirement | ≥2.5≥2.5 | ≥100≥100 |
Claims (9)
- 一种生物环氧沥青，其特征在于，包括A、B和C三个组分，A组分包括环氧大豆油和稀释剂，B组分包括固化剂、促进剂和消泡剂，C组分包括沥青；A biological epoxy asphalt, which is characterized in that it includes three components: A, B, and C; component A includes epoxy soybean oil and diluent; component B includes a curing agent, an accelerator, and an antifoaming agent; and group C Points include asphalt;其中，A组分与B组分的质量比为105～126：45，A组分和B组分的质量之和与C组分的质量的比为100：57～520；Among them, the mass ratio of the A component and the B component is 105 to 126: 45, and the ratio of the sum of the masses of the A component and the B component to the mass of the C component is 100: 57 to 520;其中，A组分中，环氧大豆油和稀释剂的质量比为100：10～30；B组分中，固化剂、促进剂和消泡剂的质量比为45：0.5～1：0.6～1。Among them, in the component A, the mass ratio of the epoxy soybean oil and the diluent is 100: 10 to 30; in the component B, the mass ratio of the curing agent, the accelerator and the defoaming agent is 45: 0.5 to 1: 0.6 to 1.
- 根据权利要求1所述的生物环氧沥青，其特征在于，所述的稀释剂为环氧树脂活性稀释剂。The bio-epoxy asphalt according to claim 1, wherein the diluent is an epoxy resin reactive diluent.
- 根据权利要求1所述的生物环氧沥青，其特征在于，所述的固化剂为长链脂肪族伯胺。The bio-epoxy pitch according to claim 1, wherein the curing agent is a long-chain aliphatic primary amine.
- 根据权利要求1所述的生物环氧沥青，其特征在于，所述的促进剂为芳香胺或碱。The biological epoxy asphalt according to claim 1, wherein the accelerator is an aromatic amine or a base.
- 根据权利要求1所述的生物环氧沥青，其特征在于，所述的消泡剂为低分子量聚醚。The biological epoxy asphalt according to claim 1, wherein the defoaming agent is a low molecular weight polyether.
- 根据权利要求1所述的生物环氧沥青，其特征在于，所述的沥青为70号道路石油沥青或90号道路石油沥青。The bio-epoxy asphalt according to claim 1, wherein the asphalt is road petroleum asphalt No. 70 or road petroleum asphalt No. 90.
- 权利要求1所述的生物环氧沥青的制备方法，其特征在于，它包括如下步骤：The method for preparing biological epoxy asphalt according to claim 1, characterized in that it comprises the following steps:(1)A组分的制备：将配方量的环氧大豆油和稀释剂混合均匀后，加热至160±2℃，搅拌反应100～140min后，在室温下冷却23～25h，即得生物环氧沥青A组分；(1) Preparation of component A: After mixing the formulated amounts of epoxy soybean oil and diluent, heat to 160 ± 2 ℃, stir for 100 ～ 140min, and then cool for 23 ～ 25h at room temperature to obtain the biological ring. A component of oxygen pitch;(2)B组分的制备：将配方量的固化剂、促进剂和消泡剂混合均匀后，加热至98～102℃后，充分反应27～33min后再冷却至室温，即得生物环氧沥青B组分；(2) Preparation of component B: After mixing the formulating amount of curing agent, accelerator and defoaming agent uniformly, heating to 98-102 ° C, fully reacting for 27-33min, and then cooling to room temperature to obtain biological epoxy Asphalt B component;(3)将加热至58～62℃的步骤(1)中制备得到的A组分倒入加热至58～62℃的步骤(2)中制备得到的B组分中，混合均匀后倒入加热至148～152℃的C组分中，混合均匀后经固化得到生物环氧沥青。(3) Pour component A prepared in step (1) heated to 58-62 ° C into component B prepared in step (2) heated to 58-62 ° C, mix well and pour into heat In the component C to 148 to 152 ° C, after being mixed uniformly, the epoxy epoxy asphalt is obtained by curing.
- 根据权利要求7所述的制备方法，其特征在于，步骤(3)中，所述的固化条件为58～62℃下固化70～74h。The preparation method according to claim 7, characterized in that, in step (3), the curing conditions are curing at 58-62 ° C for 70-74h.
- 权利要求1所述的生物环氧沥青在制备环氧沥青混合料中的应用。The use of the biological epoxy asphalt according to claim 1 in preparing an epoxy asphalt mixture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605845A (en) * | 2022-04-02 | 2022-06-10 | 郑州中科新兴产业技术研究院 | Microcapsule controllable curing cold-mix epoxy asphalt and preparation method and application thereof |
| CN114621595A (en) * | 2022-03-22 | 2022-06-14 | 江西省交通科学研究院有限公司 | Environment-friendly cold-mixed epoxy asphalt and preparation method and application thereof |
| CN115073061A (en) * | 2022-05-12 | 2022-09-20 | 福建农林大学 | Regenerated asphalt mixture and preparation method thereof |
| CN115216159A (en) * | 2022-07-29 | 2022-10-21 | 邰惠仙 | Oil-proof high-temperature-resistant asphalt and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521760A (en) * | 2019-09-17 | 2021-03-19 | 上海雁岛实业有限公司 | Anti-ice-freezing environment-friendly diluted asphalt and preparation method thereof |
| CN111518404B (en) * | 2020-05-27 | 2022-05-27 | 哈尔滨工业大学 | Environment-friendly warm-mix asphalt regenerant and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB949717A (en) * | 1960-04-28 | 1964-02-19 | Shell Int Research | Polyepoxide-bitumen compositions |
| CN103881745A (en) * | 2014-04-01 | 2014-06-25 | 中交瑞通路桥养护科技有限公司 | Coal asphalt material for paving high-grade road and preparation method of coal asphalt material |
| CN104031396A (en) * | 2013-11-20 | 2014-09-10 | 湖北大学 | Cold mixing epoxy asphalt material and preparation method thereof |
| CN105419233A (en) * | 2015-12-04 | 2016-03-23 | 长安大学 | Epoxy resin curing material system for high-temperature mixed epoxy asphalt and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585528B (en) * | 2012-02-23 | 2014-03-12 | 南京大学 | High-performance epoxy bitumen mixture easy to construct and maintain and preparation method thereof |
| CN103113752A (en) * | 2013-03-05 | 2013-05-22 | 南京大学 | High-performance epoxy resin asphalt warm mixing agent and preparation method thereof |
| CN103497487A (en) * | 2013-09-30 | 2014-01-08 | 南京大学 | Cold mix epoxy resin material for quickly repairing epoxy asphalt pavement pits as well as preparation method and application thereof |
| CN104031395B (en) * | 2013-11-20 | 2019-05-21 | 湖北大学 | A kind of bituminous epoxy expanding material and preparation method thereof and application method |
| CN103834186B (en) * | 2014-03-25 | 2016-01-20 | 南京仁恒路桥科技有限公司 | A kind of warm mix fast curable epoxy bituminous material and preparation method thereof |
-
2018
- 2018-05-23 CN CN201810498763.1A patent/CN108892956B/en active Active
- 2018-09-21 WO PCT/CN2018/106861 patent/WO2019223201A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB949717A (en) * | 1960-04-28 | 1964-02-19 | Shell Int Research | Polyepoxide-bitumen compositions |
| CN104031396A (en) * | 2013-11-20 | 2014-09-10 | 湖北大学 | Cold mixing epoxy asphalt material and preparation method thereof |
| CN103881745A (en) * | 2014-04-01 | 2014-06-25 | 中交瑞通路桥养护科技有限公司 | Coal asphalt material for paving high-grade road and preparation method of coal asphalt material |
| CN105419233A (en) * | 2015-12-04 | 2016-03-23 | 长安大学 | Epoxy resin curing material system for high-temperature mixed epoxy asphalt and preparation method thereof |
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| CN114621595A (en) * | 2022-03-22 | 2022-06-14 | 江西省交通科学研究院有限公司 | Environment-friendly cold-mixed epoxy asphalt and preparation method and application thereof |
| CN114605845A (en) * | 2022-04-02 | 2022-06-10 | 郑州中科新兴产业技术研究院 | Microcapsule controllable curing cold-mix epoxy asphalt and preparation method and application thereof |
| CN115073061A (en) * | 2022-05-12 | 2022-09-20 | 福建农林大学 | Regenerated asphalt mixture and preparation method thereof |
| CN115073061B (en) * | 2022-05-12 | 2023-02-10 | 福建农林大学 | Regenerated asphalt mixture and preparation method thereof |
| CN115216159A (en) * | 2022-07-29 | 2022-10-21 | 邰惠仙 | Oil-proof high-temperature-resistant asphalt and preparation method thereof |
Also Published As
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| CN108892956A (en) | 2018-11-27 |
| CN108892956B (en) | 2022-02-11 |
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