Low-temperature cured bio-based high-toughness epoxy asphalt material and preparation method thereof

Abstract

A low-temperature cured bio-based high-toughness epoxy asphalt material relates to the technical field of preparation of road engineering materials, and is prepared from the following raw materials in parts by mass: bisphenol A type epoxy resin, bio-based epoxy resin, a biogenic amine curing agent, an epoxy diluent, a catalyst and matrix asphalt. The asphalt comprises the following components in parts by weight: 15-30 parts of bisphenol A type epoxy resin, 5-18 parts of bio-based epoxy resin, 10-20 parts of a biogenic amine curing agent, 1-5 parts of an epoxy diluent, 0.5-3 parts of a catalyst and 35-55 parts of matrix asphalt. The preparation method of the low-temperature cured bio-based high-toughness epoxy asphalt material comprises four steps. The preparation raw materials mainly come from renewable biomass resources, the production does not depend on non-renewable petroleum resources, and the prepared finished product has good degradability, reduces the risk of environmental pollution, has certain chemical stability and physical properties, and is suitable for industrial production. The pavement performance such as high-temperature rut resistance, low-temperature crack resistance and water damage resistance of the road asphalt mixture can be improved, and the overall quality of the road mixture can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of road engineering material preparation, in particular to a low-temperature curing bio-based high-toughness epoxy asphalt material and a preparation method thereof. Background Art

[0002] Epoxy asphalt, a high-performance composite material, combines the advantages of epoxy resin and asphalt. In engineering applications, it offers excellent high-temperature rutting resistance, durable anti-skid properties, a long lifespan, and low maintenance. While existing epoxy asphalts meet engineering needs to a certain extent, they also suffer from several technical drawbacks due to limitations in materials and manufacturing processes. First, this material relies heavily on non-renewable petroleum-based raw materials, such as bisphenol A epoxy resin and petroleum-based curing agents, and its production process is associated with significant carbon emissions. Second, its construction adaptability is limited. In low-temperature environments (especially severe cold), the material requires high temperatures for effective curing. This not only leads to a sharp increase in construction energy consumption and a significant decrease in curing reaction efficiency, but also inevitably prolongs the construction period. Furthermore, the production and paving process releases large amounts of volatile organic compounds (VOCs), causing environmental pollution. Furthermore, the discarded material is difficult to biodegrade, further exacerbating the ecological burden. Finally, the toughness of traditional epoxy asphalt materials decreases significantly in low-temperature environments, becoming brittle. When used in road construction, it can easily induce road cracking, seriously damaging the integrity of the road structure and thus shortening the service life of the road.

[0003] Faced with the challenges of global climate change and the urgent need for green infrastructure upgrades, the development of high-performance bio-based road materials is an inevitable choice for the transportation infrastructure industry to achieve a green and low-carbon transformation. Bio-based epoxy asphalt materials utilize renewable biomass resources to partially or completely replace traditional petroleum-based epoxy resins and curing agents, reducing dependence on fossil resources at the source. However, existing technologies lack the application of bio-based epoxy resins in epoxy asphalt pavement materials; there is also a lack of sustainable epoxy asphalt materials that can be cured at low temperatures and exhibit high toughness. Therefore, it is necessary to provide an epoxy asphalt material that can be cured at low temperatures and exhibits high toughness, as well as a preparation method. Summary of the Invention

[0004] In order to overcome the drawbacks of existing epoxy asphalt due to limitations in its composition and preparation process, as described in the background art, the present invention provides a low-temperature curing bio-based high-toughness epoxy asphalt material and preparation method that can improve the adhesion, flexibility and other properties of road mixtures, thereby helping to improve the overall quality of road mixtures.

[0005] The technical solution adopted by the present invention to solve its technical problem is: A low-temperature curing bio-based high-toughness epoxy asphalt material, the raw materials include bisphenol A epoxy resin, bio-based epoxy resin, biogenic amine curing agent, epoxy diluent, catalyst, base asphalt, by mass, bisphenol A epoxy resin is 15-30 parts, bio-based epoxy resin is 5-18 parts, biogenic amine curing agent is 10-20 parts, epoxy diluent is 1-5 parts, catalyst is 0.5-3 parts, base asphalt is 35-55 parts; the bisphenol A epoxy resin is E51, E44, E20; the bio-based epoxy resin is at least one of lignin-based epoxy resin and epoxy soybean oil; the biogenic amine curing agent is one or more combinations of pepperethylamine, spermidine trihydrochloride, cardanol amine, and rosin amine; the epoxy diluent is one or more combinations of cardanol glycidyl ether, propenyl glycidyl ether, and butyl glycidyl ether; the catalyst is one or more combinations of 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole), 2, 4, 6-tris(dimethylaminomethyl)phenol; the matrix asphalt is 70A matrix asphalt.

[0006] Furthermore, the bisphenol A epoxy resin is a mixture of E51 and E44, and the mass ratio of E51 to E44 in the mixture is 1:0.6~1.

[0007] Furthermore, the bio-based epoxy resin is a mixture of lignin-based epoxy resin and epoxy soybean oil, and the mass ratio of the lignin-based epoxy resin to the epoxy soybean oil in the mixture is 1:0.5~1.

[0008] Furthermore, the biogenic amine curing agent is a mixture of piperonyl ethylamine, spermidine trihydrochloride, cardanolamine and rosinamine, and the mass ratio of spermidine trihydrochloride, cardanolamine and rosinamine in the mixture is 1-5:2~4:5~7:1~2.

[0009] Furthermore, the epoxy diluent is a mixture of cardanol glycidyl ether and butyl glycidyl ether; the mass ratio of cardanol glycidyl ether to butyl glycidyl ether in the mixture is 2-4:0.5-1.

[0010] Furthermore, the catalyst is a mixture of 2-ethyl-4-methylimidazole and 2, 4, 6-tris(dimethylaminomethyl)phenol; the mass ratio of EMI to DMP-30 in the mixture is 0.5-1:1.5-2.5.

[0011] A method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material comprises the following steps: S1: preparing bisphenol A epoxy resin, bio-based epoxy resin, biogenic amine curing agent, epoxy diluent, catalyst, and matrix asphalt material respectively in proportion, and fully mixing the bisphenol A epoxy resin, bio-based epoxy resin, and epoxy diluent to obtain component A for standby use; S2: preheating the matrix asphalt to 110-130°C for standby use; S3: fully mixing the biogenic amine curing agent and the catalyst to obtain component B for standby use; S4: fully mixing components A and B, and then adding them together with the matrix asphalt into a mixing device, stirring them evenly, pouring them into a mold, and curing them at room temperature to obtain a finished product.

[0012] Furthermore, in step S4, the mixing ratio of component A to component B is 3-4:2-3.

[0013] Furthermore, in step S4, the mass ratio of the mixture of components A and B to the matrix asphalt is 3~4:6~7.

[0014] Furthermore, the stirring speed in step S4 is in the range of 400-600 rpm, and the specific time is 5-15 min.

[0015] Furthermore, the room temperature in step S4 is in the range of 27-40° C., and the curing time is 2-3 days.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: the low-temperature curing bio-based high-toughness epoxy asphalt material finished product prepared by the present invention is mainly used in the field of road engineering material technology and is used for paving low-temperature sustainable roads; the bio-based epoxy resin used as a basic material has many significant advantages in the field of road engineering materials. First, its raw materials are mainly derived from renewable biomass resources, such as plant oils or lignin, which makes the production of bio-based resins independent of non-renewable petroleum resources and conforms to the concept of sustainable development; secondly, bio-based resins usually have good degradability and can gradually decompose in the natural environment after their service life ends, reducing the risk of long-term pollution to the environment; in addition, bio-based resins also have certain chemical stability and physical properties. Combined with all other materials, they can improve the adhesion, flexibility, low-temperature curing and other properties of road mixtures, which helps to improve the overall quality of road mixtures. In summary, the present invention has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a schematic flow chart of a method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material according to the present invention. DETAILED DESCRIPTION

[0018] A low-temperature curing, bio-based, high-toughness epoxy asphalt material. Its raw materials include bisphenol A epoxy resin, bio-based epoxy resin, biogenic amine curing agent, epoxy diluent, catalyst, and base asphalt. The epoxy resin and curing agent react to form a high-strength, corrosion-resistant, rigid network structure. The epoxy diluent improves the compatibility between the asphalt and the resin. The catalyst promotes the complete formation of a cross-linked network at low temperatures. The base asphalt, as a flexible component, imparts flexibility to the material.

[0019] Example 1: Figure 1 As shown, a method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material comprises the following steps: (1) preparing component A: specifically, by mass, taking 20 parts of bisphenol A epoxy resin, including 14 parts of E51 and 6 parts of E44; taking 18 parts of biomass epoxy resin, including 12 parts of lignin-based epoxy resin and 6 parts of epoxidized soybean oil; taking 5 parts of epoxy diluent, including 4 parts of CGE and 1 part of BGE; and fully mixing the above three. (2) heating the base asphalt to 120°C and setting aside. (3) preparing component B: specifically, taking 21 parts of biogenic amine curing agent, including 3 parts of piperonyl ethylamine, 5 parts of spermidine trihydrochloride, 12 parts of cardanol amine and 4 parts of rosin amine; taking 2.5 parts of catalyst, including 1 part of EMI and 1.5 parts of DMP-30; and fully mixing the above two. (4) Components A and B are fully mixed, and then added into the mixing equipment together with 55 parts of base asphalt. After stirring evenly, pour into the mold and cure at room temperature. The specific speed range is 400~600 rpm, the specific temperature is 27℃, and the specific curing time is 0.5 days.

[0020] Example 2: Figure 1 As shown, a method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material includes the following steps: (1) preparing component A: specifically, by mass, taking 16 parts of bisphenol A epoxy resin, including 10 parts of E51 and 6 parts of E44; taking 15 parts of biomass epoxy resin, including 10 parts of lignin-based epoxy resin and 5 parts of epoxidized soybean oil; taking 4 parts of epoxy diluent, including 3 parts of CGE and 1 part of BGE; and fully mixing the above three. (2) heating the base asphalt to 120°C and setting aside. (3) preparing component B: specifically, taking 15 parts of biogenic amine curing agent, including 4 parts of spermidine trihydrochloride, 10 parts of cardanol amine and 1 part of rosin amine; taking 2 parts of catalyst, including 0.8 parts of EMI and 1.2 parts of DMP-30; and fully mixing the above two. (4) Components A and B are fully mixed, and then added into the mixing equipment together with 50 parts of base asphalt. After stirring evenly, pour into the mold and cure at room temperature. The specific speed range is 400~600 rpm, the specific temperature is 27℃, and the specific curing time is 1.5 days.

[0021] Example 3: Figure 1As shown, a method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material includes the following steps: (1) preparing component A: specifically, by mass, taking 22 parts of bisphenol A epoxy resin, including 11 parts of E51 and 11 parts of E44; taking 10 parts of biomass epoxy resin, including 5 parts of lignin-based epoxy resin and 5 parts of epoxidized soybean oil; taking 2.8 parts of epoxy diluent, including 2.1 parts of CGE and 0.7 parts of BGE; and fully mixing the above three. (2) heating the base asphalt to 120°C and setting aside. (3) preparing component B: taking 15 parts of biogenic amine curing agent, including 4 parts of spermidine trihydrochloride, 9 parts of cardanol amine and 2 parts of rosin amine; taking 1.5 parts of catalyst, including 0.5 parts of EMI and 1 part of DMP-30; and fully mixing the above two. (4) Components A and B are fully mixed, and then added into the mixing equipment together with 50 parts of base asphalt. After stirring evenly, pour into the mold and cure at room temperature. The specific speed range is 400~600 rpm, the specific temperature is 27℃, and the specific curing time is 2.5 days.

[0022] Comparative Example 1: A method for preparing an epoxy asphalt pavement material without a bio-based epoxy resin comprises the following steps: (1) preparing component A: taking 38 parts by mass of bisphenol A epoxy resin, including 26 parts of E51 and 12 parts of E44; taking 5 parts of epoxy diluent, including 4 parts of CGE and 1 part of BGE; and fully mixing the above two. (2) heating the base asphalt to 120°C for standby use. (3) preparing component B: taking 21 parts of a biogenic amine curing agent, including 5 parts of spermidine trihydrochloride, 12 parts of cardanolamine and 4 parts of rosinamine; taking 2.5 parts of a catalyst, including 1 part of EMI and 1.5 parts of DMP-30; and fully mixing the above two. (4) fully mixing components A and B, and then adding them together with 55 parts of the base asphalt into a mixing device, stirring evenly, pouring into a mold, and curing at room temperature. The specific speed range is 400-600 rpm, the specific temperature is 27°C, and the specific curing time is 2.5 days.

[0023] Comparative Example 2: A method for preparing a bio-based epoxy asphalt pavement material cured with a single biogenic amine curing agent, comprising the following steps: (1) preparing component A: taking 16 parts by mass of bisphenol A epoxy resin, including 10 parts of E51 and 6 parts of E44; taking 15 parts of biomass epoxy resin, including 10 parts of lignin-based epoxy resin and 5 parts of epoxidized soybean oil; taking 4 parts of epoxy diluent, including 3 parts of CGE and 1 part of BGE; and fully mixing the above three. (2) heating the base asphalt to 120°C and setting aside. (3) preparing component B: taking 15 parts of spermidine trihydrochloride; taking 2 parts of catalyst, including 0.8 parts of EMI and 1.2 parts of DMP-30; and fully mixing the above two. (4) fully mixing components A and B, and then adding them together with 50 parts of base asphalt into a mixing device, stirring evenly, pouring into a mold, and curing at room temperature. The specific speed range is 400~600 rpm, the specific temperature is 27°C, and the specific curing time is 2.5 days.

[0024] The following content is the epoxy asphalt materials prepared by Examples 1 to 3 and Comparative Examples 1 to 2. After curing, the performance test was immediately carried out. The test results are shown in Table 1.

[0025] The test methods mentioned in the table involve the following data: (1) Tensile strength. Tensile strength is the maximum stress value (unit: MPa) that characterizes the resistance of epoxy asphalt materials to fracture under axial tensile load, which directly determines the pavement's ability to resist structural cracking. The test method is as follows: The tensile strength test of epoxy asphalt specimens is mainly carried out in accordance with the corresponding requirements of [Vulcanized rubber or thermoplastic rubber. Determination of tensile stress-strain properties] (GB / T 528); first, epoxy asphalt specimens that meet the specified dimensions are carefully prepared and placed in a constant temperature environment at 25°C for 0.5-3 days to ensure that the specimen performance is stable and reaches the temperature conditions required for the test; the key parts such as the clamps of the tensile testing equipment are also adjusted to the same temperature state as the specimen; then the loading system is started to subject the specimen to a tensile load at a loading rate of 100 mm / min; through the connected high-precision sensors and data acquisition system, the stress changes and corresponding deformation data of the specimen during the stress process are recorded in real time and automatically stored in the supporting computer software; when the specimen is stretched to break, the tensile testing machine automatically stops running, and the tensile strength value of the epoxy asphalt specimen is clearly displayed on the computer interface.

[0026] (2) Elongation at break. Specifically, elongation at break directly reflects the degree of deformation that epoxy asphalt can withstand when subjected to tensile force until it breaks. Its magnitude is affected by factors such as the material's flexibility and the mobility of the molecular chains. It is of great significance for understanding the deformation adaptability of epoxy asphalt during actual use. The test method is as follows: The elongation at break test of epoxy asphalt specimens is carried out in accordance with the provisions of [Vulcanized rubber or thermoplastic rubber. Determination of tensile stress-strain properties] (GB / T 528). After the epoxy asphalt specimens of standard shape and size are accurately prepared, they are also placed in a constant temperature field at 25°C for preheating or precooling to the specified time of 0.5-3 days to ensure that the entire specimen is in a uniform and stable temperature field; the various components of the tensile testing device are subjected to corresponding temperature adaptation treatments to match the specimen temperature; the loading device is turned on, and a tensile load is slowly applied to the specimen, maintaining a loading rate of 100 mm / min; with the help of advanced measuring tools such as optical extensometers or electronic extensometers, the length changes of the specimen during the stretching process are closely tracked, and the relevant data are transmitted in real time to the professional analysis software in the computer; until the specimen breaks, the testing machine stops loading, and the software automatically calculates and displays the specific value of the elongation at break of the epoxy asphalt specimen.

[0027] (3) -10℃ tensile strength and elongation specifically measure the ability of epoxy asphalt materials to withstand bending deformation in low-temperature environments. They are closely related to the material's brittleness, toughness balance, and internal structural stability at low temperatures. They are important considerations in the construction and maintenance of epoxy asphalt-related facilities in cold regions. The test method is as follows: Conduct a -10℃ bending strain test on epoxy asphalt specimens in strict accordance with [Rubber vulcanized or thermoplastic rubber. Determination of tensile stress-strain properties] (GB / T 528). Epoxy asphalt specimens that meet standard size requirements are carefully made and quickly transferred to a low-temperature test chamber that has been precisely controlled to -20°C and left for 6 hours to ensure that the specimens are fully adapted to the low-temperature environment and the temperature distribution is uniform; at the same time, the various components of the bending test device are also placed in the low-temperature environment for pre-cooling to ensure that they are at the same temperature as the specimens; then the loading mechanism is started to subject the specimens to a bending load at a loading rate of 100 mm / min; a high-precision displacement sensor is used to monitor the deformation of the specimens during the bending process in real time, and the data is simultaneously fed back to the connected computer data processing system; when the specimen is bent to a certain extent (the corresponding deformation amount is reached according to the standard or signs of damage appear), the bending test device automatically stops loading, and the computer calculates and displays the tensile strength and elongation of the epoxy asphalt specimens at -10°C based on the recorded data.

[0028] Table 1 Performance comparison of the examples of the present invention and the comparative examples

[0029] As can be seen in Table 1, Examples 1-3 exhibit excellent overall performance across all performance indicators. This is attributed to the use of bio-based epoxy resin and biogenic amine curing agent, as well as the optimal raw material ratios and mixing process. While varying raw material selection and ratio adjustments can lead to some fluctuation in performance indicators, these indicators are still maintained at a good level, meeting the requirements for low-temperature, high-performance, sustainable road materials. Comparative Example 1, which does not utilize a bio-based epoxy resin, exhibits significantly lower performance indicators than the Examples. This demonstrates that bio-based epoxy resin plays a crucial role in improving the performance of epoxy asphalt materials, significantly enhancing their tensile strength, elongation at break, and low-temperature flexural strain. Comparative Example 2, which utilizes a single biogenic amine curing agent, also exhibits lower performance indicators than the Examples. This demonstrates that the combined use of multiple biogenic amine curing agents significantly enhances the overall performance of epoxy asphalt materials, helping to maintain their excellent performance under various operating conditions. In summary, the present invention adopts sustainably sourced bio-based epoxy resin as an effective alternative component to petroleum-based epoxy resin, and uses a bio-amine curing agent in conjunction with it, and scientifically uses a catalyst, which can significantly improve the various properties of epoxy asphalt materials and enhance their applicability for construction in low-temperature environments.

[0030] The basic principles and main features of the present invention and the advantages of the present invention are shown and described above. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive. The scope of the present invention is defined by the appended claims rather than the foregoing description, and all changes that come within the meaning and range of equivalents of the claims are intended to be included therein.

[0031] In addition, it should be understood that although this specification is described in terms of implementation methods, the implementation methods do not only include an independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A low-temperature curing bio-based high-toughness epoxy asphalt material, characterized in that: The raw materials include bisphenol A epoxy resin, bio-based epoxy resin, biogenic amine curing agent, epoxy diluent, catalyst, and matrix asphalt. By mass, the bisphenol A epoxy resin is 15-30 parts, the bio-based epoxy resin is 5-18 parts, the biogenic amine curing agent is 10-20 parts, the epoxy diluent is 1-5 parts, the catalyst is 0.5-3 parts, and the matrix asphalt is 35-55 parts; the bisphenol A epoxy resin is one or more of E51, E44, and E20. combinations; the bio-based epoxy resin is at least one of lignin-based epoxy resin and epoxy soybean oil; the biogenic amine curing agent is one or more combinations of pepperethylamine, spermidine trihydrochloride, cardanol amine, and rosin amine; the epoxy diluent is one or more combinations of cardanol glycidyl ether, propenyl glycidyl ether, and butyl glycidyl ether; the catalyst is one or more combinations of 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and 2, 4, 6-tris(dimethylaminomethyl)phenol; the matrix asphalt is 70# matrix asphalt.

2. The low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 1, characterized in that: The bisphenol A epoxy resin is a mixture of E51 and E44, and the mass ratio of E51 to E44 in the mixture is 1:0.6~1.

3. The low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 1, characterized in that: The bio-based epoxy resin is a mixture of lignin-based epoxy resin and epoxidized soybean oil, and the mass ratio of the lignin-based epoxy resin to the epoxidized soybean oil in the mixture is 1:0.5~1.

4. The low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 1, characterized in that: The biogenic amine curing agent is a mixture of piperonyl ethylamine, spermidine trihydrochloride, cardanolamine and rosinamine, wherein the mass ratio of spermidine trihydrochloride, cardanolamine and rosinamine in the mixture is 1-5:2-4:5-7:1-2.

5. The low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 1, characterized in that: The epoxy diluent is a mixture of cardanol glycidyl ether and butyl glycidyl ether; the mass ratio of cardanol glycidyl ether to butyl glycidyl ether in the mixture is 2-4:0.5-1.

6. The low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 1, characterized in that: The catalyst is a mixture of 2-ethyl-4-methylimidazole and 2, 4, 6-tris(dimethylaminomethyl)phenol; the mass ratio of EMI to DMP-30 in the mixture is 0.5-1:1.5-2.

5.

7. The method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: S1: preparing bisphenol A epoxy resin, bio-based epoxy resin, biogenic amine curing agent, epoxy diluent, catalyst and matrix asphalt material respectively in proportion, and fully mixing the bisphenol A epoxy resin, bio-based epoxy resin and epoxy diluent to obtain component A for standby use; S2: preheating the matrix asphalt to 110-130°C for standby use; S3: fully mixing the biogenic amine curing agent and the catalyst to obtain component B for standby use; S4: fully mixing components A and B, and then adding them together with the matrix asphalt into a mixing device, stirring evenly, pouring into a mold, and curing at room temperature to obtain a finished product.

8. The method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 6, characterized in that: In step S4, the mixing ratio of component A to component B is 3~4:2~3; the mass ratio of the mixture of components A and B to the matrix asphalt is 3~4:6~7.

9. The method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 6, characterized in that: In the step S4, the stirring speed ranges from 400 to 600 rpm, and the specific stirring time is 5 to 15 minutes.

10. The method for preparing a low-temperature curing bio-based high-toughness epoxy asphalt material according to claim 6, characterized in that: In step S4, the room temperature range is 27-40° C., and the curing time is 0.5-3 days.

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