High-performance epoxy asphalt material and preparation method thereof

Abstract

The invention relates to the technical field of epoxy asphalt material processing, in particular to a high-performance epoxy asphalt material and a preparation method thereof.The high-performance epoxy asphalt material comprises a component A, a component B and a component C. The component A is TPU modified asphalt, the component B is TPU-g-MWNTs modified epoxy resin, and the component C is a curing agent. But the MWNTs have weak surface chemical inertness and interface bonding force, so that the application of the MWNTs is limited, and TPU is adopted to perform surface modification on the MWNTs, so that not only are the dispersity and interface bonding property of the MWNTs and epoxy asphalt improved, but also the MWNTs serving as a flexible chain segment can further toughen the epoxy asphalt and improve the cracking resistance and fatigue durability of the epoxy asphalt material; and the service life is prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy asphalt material processing, and particularly relates to a high-performance epoxy asphalt material and a preparation method thereof. Background Art

[0002] The epoxy asphalt paving system has excellent mechanical properties and high-temperature stability, and has been widely promoted and applied in many steel bridge deck paving projects. It has become one of the mainstream paving schemes for steel bridge decks. This system has beneficial effects such as high strength and excellent corrosion resistance, providing good durability and stability for the bridge deck paving.

[0003] However, due to the fact that the main component of the existing epoxy asphalt material, epoxy resin, belongs to a thermosetting polymer material, it becomes brittle and has a large stiffness after chemical cross-linking, resulting in poor deformation ability and toughness. It is easy to cause early cracking of the mixture, and after cracking, it has a greater impact on the integrity of the paving, the comprehensive performance decays, and the durability decreases. This poses a challenge to the long-term service performance of the epoxy asphalt material. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-performance epoxy asphalt material and a preparation method thereof, to solve the problem in the prior art that due to the fact that the main component of the existing epoxy asphalt material, epoxy resin, belongs to a thermosetting polymer material, it becomes brittle and has a large stiffness after chemical cross-linking, resulting in poor deformation ability and toughness. It is easy to cause early cracking of the mixture, and after cracking, it has a greater impact on the integrity of the paving, the comprehensive performance decays, and the durability decreases. This poses a challenge to the long-term service performance of the epoxy asphalt material.

[0005] To achieve the above purpose, the present invention provides a high-performance epoxy asphalt material, which is composed of component A, component B and component C. Component A is TPU-modified asphalt, component B is TPU-g-MWNTs-modified epoxy resin, and component C is a curing agent.

[0006] The present invention also provides a preparation method of a high-performance epoxy asphalt material. The preparation method of the high-performance epoxy asphalt material includes the following steps:

[0007] Step S1: Add MAH-g-TPU into a toluene solvent for full swelling, add MWNTs-NH2, disperse evenly based on ultrasonic stirring, then add triethylamine for heating and stirring reaction. After the reaction is completed, remove the unreacted MAH-g-TPU, and then dry to obtain TPU-g-MWNTs;

[0008] Step S2: Then mix bisphenol A epoxy resin, glycidyl ether and flexible epoxy resin according to a weight ratio to obtain a composite epoxy resin. Finally, disperse and mix the composite epoxy resin and TPU-g-MWNTs evenly based on ultrasonic waves to obtain TPU-g-MWNTs-modified epoxy resin;

[0009] Step S3: Heat the base asphalt to 130 - 150 °C, add the terminal NCO polyurethane prepolymer and the chain extender to the base asphalt at a ratio of NCO / OH = 1, raise the temperature and stir to prepare the TPU-modified asphalt;

[0010] Step S4: Mix and stir the TPU-g-MWNTs modified epoxy resin and the curing agent according to the weight ratio to prepare the epoxy resin binder;

[0011] Step S5: Add the epoxy resin binder to the TPU-modified asphalt, raise the temperature and stir to prepare the high-performance epoxy asphalt material.

[0012] Among them, in Step S1, the temperature for adding triethylamine is 90 °C, and the stirring reaction time is 24 h.

[0013] Among them, in Step S2, the weight ratio of bisphenol A epoxy resin, glycidyl ether and flexible epoxy resin is 50 - 100:5 - 20:5 - 15.

[0014] Among them, in Step S2, the bisphenol A epoxy resin is hydrogenated bisphenol A epoxy resin, the glycidyl ether is one of diglycidyl phthalate, diglycidyl dimerate, diglycidyl sebacate, diglycidyl azelate, and the flexible epoxy resin is one of 6350, 6002, 1217.

[0015] Among them, in Step S2, the weight ratio of the composite epoxy resin and TPU-g-MWNTs is 100:0.1 - 0.5, and the dispersion mixing temperature is 40 - 60 °C, and the dispersion mixing time is 10 - 30 min.

[0016] Among them, in Step S3, the dosage of the terminal NCO polyurethane prepolymer accounts for 2 - 5% of the base asphalt, the stirring time is 30 - 60 min, the temperature rise is 130 - 150 °C, the hard segment content is 20 - 30%, and the preparation method of the terminal NCO polyurethane prepolymer is to place the polyolefin polyol in a four-necked flask, stir under a nitrogen atmosphere, slowly add the measured polyisocyanate, control the temperature at 70 - 90 °C, and obtain the terminal NCO polyurethane prepolymer after reacting for 2 - 4 h.

[0017] Among them, in Step S4, the weight ratio of the TPU-g-MWNTs modified epoxy resin and the curing agent is 50 - 90:50 - 100, and the stirring time after mixing is 3 - 5 min.

[0018] Among them, in step S4, the curing agent is composed of a long carbon chain unsaturated primary amine and a terminal amino carbamate prepolymer mixed and stirred. The weight ratio of the long carbon chain unsaturated primary amine to the terminal amino carbamate prepolymer is 70-120:10-30:10-20, and the mixing and stirring time is 10-30 min.

[0019] Among them, in step S5, the heating temperature is 130-150 °C, the stirring time is 3-5 min, and the total mass of the TPU-g-MWNTs modified epoxy resin and the curing agent accounts for 45-55% of the weight of the high-performance epoxy asphalt. At the same time, the TPU in the TPU-g-MWNTs is the same as the TPU in the TPU modified asphalt.

[0020] A high-performance epoxy asphalt material and a preparation method thereof according to the present invention include component A, component B, and component C. Component A is TPU modified asphalt, component B is TPU-g-MWNTs modified epoxy resin, and component C is a curing agent. Although using MWNTs to modify epoxy asphalt has good toughening effects, its surface chemical inertness and weak interfacial bonding force limit its application. Then, using TPU to modify the surface of MWNTs not only improves its dispersibility and interfacial bonding with epoxy asphalt, but also, as a flexible chain segment itself, can further toughen epoxy asphalt; using TPU can improve the compatibility between epoxy resin and asphalt, further playing a role in toughening and softening, thereby enabling the epoxy asphalt concrete to have excellent crack resistance and fatigue durability and extending its service life. Brief Description of the Drawings

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0022] Figure 1 is a flowchart of the steps of the preparation method of the high-performance epoxy asphalt material provided by the present invention.

[0023] Figure 2 is a molecular structure diagram of the terminal amino carbamate prepolymer in the preparation method of the high-performance epoxy asphalt material provided by the present invention. Detailed Embodiments

[0024] Embodiments of the present invention will be described in detail below. Examples of the embodiments are shown in the accompanying drawings, where the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.

[0025] Please refer to Figures 1 to 2 , the present invention provides a high-performance epoxy asphalt material, which consists of component A, component B and component C. Component A is TPU-modified asphalt, component B is TPU-g-MWNTs-modified epoxy resin, and component C is a curing agent.

[0026] The present invention also provides a method for preparing a high-performance epoxy asphalt material. The method for preparing the high-performance epoxy asphalt material includes the following steps:

[0027] Step S1: Add MAH-g-TPU into toluene solvent for sufficient swelling, add MWNTs-NH2, disperse evenly based on ultrasonic stirring, then add triethylamine for heating and stirring reaction. After the reaction is completed, remove the unreacted MAH-g-TPU, and then dry to obtain TPU-g-MWNTs;

[0028] Step S2: Then mix bisphenol A-type epoxy resin, glycidyl ether and flexible epoxy resin according to a weight ratio to obtain a composite epoxy resin. Finally, disperse and mix the composite epoxy resin and TPU-g-MWNTs evenly based on ultrasonic waves to obtain TPU-g-MWNTs-modified epoxy resin;

[0029] Step S3: Heat the base asphalt to 130 - 150 °C, add the terminal NCO polyurethane prepolymer and the chain extender to the base asphalt at a ratio of NCO / OH = 1 for heating and stirring to prepare TPU-modified asphalt;

[0030] Step S4: Mix and stir the TPU-g-MWNTs-modified epoxy resin and the curing agent according to a weight ratio to prepare an epoxy resin binder;

[0031] Step S5: Add the epoxy resin binder to the TPU-modified asphalt, heat up and stir to prepare a high-performance epoxy asphalt material.

[0032] In this embodiment, although using MWNTs to modify epoxy asphalt has good toughening effects, its surface chemical inertness and weak interfacial bonding force limit its application. Then, using TPU to modify the surface of MWNTs can not only improve its dispersibility and interfacial bonding property with epoxy asphalt, but also further toughen epoxy asphalt as its own flexible chain segments; using TPU can improve the compatibility between epoxy resin and asphalt, further playing the role of toughening and softening, and then making the epoxy asphalt concrete have excellent crack resistance and fatigue durability, and extending its service life.

[0033] Among them, in step S1, the temperature for adding triethylamine is 90 °C, and the stirring reaction time is 24 h, which is beneficial to precisely control the preparation reaction of TPU-g-MWNTs, ensure the full progress of the reaction, and improve the quality and performance of the product.

[0034] Among them, in step S2, the weight ratio of bisphenol A epoxy resin, glycidyl ether, and flexible epoxy resin is 50 - 100:5 - 20:5 - 15. By optimizing the formula of the composite epoxy resin, the properties of the material, such as toughness and strength, can be adjusted to better meet different usage requirements.

[0035] Among them, in step S2, the bisphenol A epoxy resin is hydrogenated bisphenol A epoxy resin, the glycidyl ether is one of diglycidyl phthalate, diglycidyl dimerate, diglycidyl sebacate, and diglycidyl azelate, and the flexible epoxy resin is one of 6350, 6002, and 1217.

[0036] Among them, in step S2, the weight ratio of the composite epoxy resin to TPU-g-MWNTs is 100:0.1 - 0.5, and the dispersion mixing temperature is 40 - 60 °C, and the dispersion mixing time is 10 - 30 min. Through reasonable weight ratio and dispersion conditions, it can ensure the uniform dispersion of TPU-g-MWNTs in the composite epoxy resin, improve the overall performance of the material, such as enhancing the mechanical properties and electrical conductivity of the material, etc.

[0037] Among them, in step S3, the dosage of the terminal NCO polyurethane prepolymer accounts for 2 - 5% of the matrix asphalt, the stirring time is 30 - 60 min, the heating temperature is 130 - 150 °C, the hard segment content is 20 - 30%, and the preparation method of the terminal NCO polyurethane prepolymer is to place polyolefin polyol in a four-necked flask, stir under a nitrogen atmosphere, slowly add a measured amount of polyisocyanate, control the temperature at 70 - 90 °C, and obtain the terminal NCO polyurethane prepolymer after reacting for 2 - 4 h. By adjusting parameters such as the dosage of the terminal NCO polyurethane prepolymer, stirring time, heating temperature, and hard segment content, the properties of the TPU-modified asphalt can be adjusted.

[0038] Among them, in step S4, the weight ratio of the TPU-g-MWNTs modified epoxy resin to the curing agent is 50-90:50-100, and the stirring time after mixing is 3-5 min. By means of a reasonable weight ratio and stirring time, it can be ensured that the TPU-g-MWNTs modified epoxy resin and the curing agent react fully, forming an epoxy resin binder with stable properties, better combining with the TPU modified asphalt, and improving the overall performance of the high-performance epoxy asphalt material.

[0039] Among them, in step S4, the curing agent is composed of a long-chain unsaturated primary amine and a terminal amino carbamate prepolymer mixed and stirred. The weight ratio of the long-chain unsaturated primary amine to the terminal amino carbamate prepolymer is 70-120:10-30:10-20, and the mixing and stirring time is 10-30 min. By optimizing the formula and preparation process of the curing agent, the curing performance and reaction activity of the curing agent can be improved, enabling the epoxy resin binder to have better curing effect and mechanical properties.

[0040] Among them, in step S5, the heating temperature is 130-150 °C, the stirring time is 3-5 min, and the total mass of the TPU-g-MWNTs modified epoxy resin and the curing agent accounts for 45-55% of the weight of the high-performance epoxy asphalt. At the same time, the TPU in the TPU-g-MWNTs is the same as the TPU in the TPU modified asphalt. Through the precise control of these parameters, it can be ensured that the epoxy resin binder and the TPU modified asphalt are fully mixed, forming a high-performance epoxy asphalt material with uniform and stable properties.

[0041] This design uses high-performance epoxy asphalt material as the binder, basalt gravel as the aggregate, and limestone powder as the filler, adopts the median value of the EA10 gradation, and the asphalt-aggregate ratio is 6.5%. High-performance epoxy asphalt concrete is prepared at 170-185 °C, and the relevant technical indicators can be tested after curing is completed.

[0042] Although the use of MWNTs modified epoxy asphalt has good toughening effect, its surface chemical inertness and weak interfacial bonding force limit its application. Then, TPU is used to modify the surface of MWNTs, which not only improves its dispersibility and interfacial bonding property with epoxy asphalt, but also, as a flexible chain segment itself, can further toughen epoxy asphalt; using TPU can improve the compatibility between epoxy resin and asphalt, further playing a role in toughening and softening, thereby enabling the epoxy asphalt concrete to have excellent crack resistance and fatigue durability, and extending its service life. At the same time, Table 1 below can be referred to.

[0043] Table 1 Results of technical indicators of high-performance epoxy asphalt materials and their concretes

[0044] Inspection items Unit The present invention The prior art Elongation at break (23°C) ％ 416 237 Retention time (170°C) min 240 180 Dynamic stability (60°C) times / mm 70000 57570 Flexural strain (-10°C) — 5823 3823 Impact toughness N·m 3.01 2.16 Number of fatigue cycles (800 microstrain) 10,000 times 270 149

[0045] The above-disclosed is only a preferred embodiment of the present invention. Of course, it cannot be used to limit the scope of the rights of the present invention. Those of ordinary skill in the art can understand all or part of the processes of implementing the above embodiments, and the equivalent changes made according to the claims of the present invention still fall within the scope covered by the invention.

Claims

1. A high-performance epoxy asphalt material, characterized in that, it comprises component A, component B and component C. Component A is TPU-modified asphalt, component B is TPU-g-MWNTs-modified epoxy resin, and component C is a curing agent.

2. A method for preparing a high-performance epoxy asphalt material, which prepares the high-performance epoxy asphalt material as claimed in claim 1, characterized in that, It includes the following steps: Step S1: Add MAH-g-TPU into toluene solvent for sufficient swelling, add MWNTs-NH2, disperse evenly based on ultrasonic stirring, then add triethylamine for heating and stirring reaction. After the reaction is completed, remove the unreacted MAH-g-TPU, and then dry it to obtain TPU-g-MWNTs; Step S2: Then mix bisphenol A epoxy resin, glycidyl ether and flexible epoxy resin according to the weight ratio to obtain a composite epoxy resin. Finally, disperse and mix the composite epoxy resin and TPU-g-MWNTs evenly based on ultrasonic waves to obtain TPU-g-MWNTs-modified epoxy resin; Step S3: Heat the base asphalt to 130-150 °C, add the terminal NCO polyurethane prepolymer and the chain extender to the base asphalt at a ratio of NCO / OH = 1 for heating and stirring to prepare TPU-modified asphalt; Step S4: Mix and stir the TPU-g-MWNTs-modified epoxy resin and the curing agent according to the weight ratio to prepare an epoxy resin binder; Step S5: Add the epoxy resin binder to the TPU-modified asphalt, heat up and stir to prepare a high-performance epoxy asphalt material.

3. The preparation method of the high-performance epoxy asphalt material according to claim 2, characterized in that, in step S1, the temperature for adding triethylamine is 90 °C, and the stirring reaction time is 24 h.

4. The preparation method of the high-performance epoxy asphalt material according to claim 3, characterized in that, in step S2, the weight ratio of bisphenol A epoxy resin, glycidyl ether and flexible epoxy resin is 50-100:5-20:5-15.

5. The preparation method of the high-performance epoxy asphalt material according to claim 4, characterized in that, in step S2, the bisphenol A epoxy resin is hydrogenated bisphenol A epoxy resin, the glycidyl ether is one of diglycidyl phthalate, diglycidyl dimerate, diglycidyl sebacate, diglycidyl azelate, and the flexible epoxy resin is one of 6350, 6002, 1217.

6. The preparation method of the high-performance epoxy asphalt material according to claim 5, characterized in that, in step S2, the weight ratio of the composite epoxy resin and TPU-g-MWNTs is 100:0.1-0.5, and the dispersion mixing temperature is 40-60 °C, and the dispersion mixing time is 10-30 min.

7. The preparation method of the high-performance epoxy asphalt material according to claim 6, characterized in that, In step S3, the dosage of the terminal NCO polyurethane prepolymer accounts for 2-5% of the matrix asphalt, the stirring time is 30-60 min, the temperature increase is 130-150 °C, the hard segment content is 20-30%, and the preparation method of the terminal NCO polyurethane prepolymer is to place polyolefin polyol in a four-necked flask, stir under a nitrogen atmosphere, slowly add a measured amount of polyisocyanate, control the temperature at 70-90 °C, and obtain the terminal NCO polyurethane prepolymer after reacting for 2-4 h.

8. The method for preparing a high-performance epoxy asphalt material according to claim 7, wherein In step S4, the weight ratio of the TPU-g-MWNTs modified epoxy resin to the curing agent is 50-90:50-100, and the stirring time after mixing is 3-5 min.

9. The method for preparing a high-performance epoxy asphalt material according to claim 8, wherein In step S4, the curing agent is composed of a long carbon chain unsaturated primary amine and a terminal amino carbamate prepolymer mixed and stirred, the weight ratio of the long carbon chain unsaturated primary amine to the terminal amino carbamate prepolymer is 70-120:10-30:10-20, and the mixing and stirring time is 10-30 min.

10. The method for preparing a high-performance epoxy asphalt material according to claim 9, wherein In step S5, the temperature increase is 130-150 °C, the stirring time is 3-5 min, and the total mass of the TPU-g-MWNTs modified epoxy resin and the curing agent accounts for 45-55% of the weight of the high-performance epoxy asphalt. At the same time, the TPU in the TPU-g-MWNTs is the same as the TPU in the TPU modified asphalt.

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