Graphene oxide composite epoxy resin modified asphalt and preparation method thereof

Abstract

The invention relates to graphene oxide composite epoxy resin modified asphalt and a preparation method thereof. The graphene oxide composite epoxy resin modified asphalt is prepared from TETA-GO, epoxy resin and asphalt according to the mass ratio of (0.75-1.5): 10: 100. Wherein the TETA-GO is obtained by introducing a triethyl tetramine group on the surface of graphene oxide. The prepared graphene oxide composite epoxy resin modified asphalt has good deformation resistance, the complex modulus is improved by 18.66%-77.03% (46 DEG C, 10 Hz) compared with a control group of epoxy resin modified asphalt, the load bearing capacity of a traditional epoxy resin modified asphalt pavement can be effectively improved, and compared with the control group of epoxy resin modified asphalt, the load bearing capacity of the traditional epoxy resin modified asphalt pavement can be effectively improved. The rut factor is improved by 48.28%-51.45% (76 DEG C, 10 rad / s), and the deformation resistance is improved by 18.66%-77.03%.

Description

Technical Field

[0001] The present invention belongs to the technical field of building materials, and particularly relates to a graphene oxide composite epoxy resin modified asphalt and a preparation method thereof. Background Art

[0002] As an important part of transportation infrastructure, bridges play an important role in the development of China's transportation. However, with the increase in traffic flow and axle load and the deterioration of climatic conditions, problems such as high-temperature rutting, cracking, and potholes have occurred on the road surfaces of some heavy-duty traffic sections and special sections, seriously affecting the service life of bridge road surfaces. This is because the thermoplasticity of traditional asphalt binders causes irreversible deformation of asphalt pavements under load and gradually accumulates, ultimately leading to damage to the pavement structure. In contrast, epoxy resin modified asphalt exhibits strong thermosetting characteristics due to its thermosetting skeleton structure and is therefore widely used in steel bridge deck paving. However, the high material cost and addition amount of epoxy resin limit its application. Therefore, how to maintain or improve the high-temperature performance of modified asphalt while reducing the material usage has become one of the current research focuses.

[0003] Graphene oxide (GO) is an inorganic nanomaterial obtained by strong acid oxidation treatment of graphene, with excellent mechanical strength and chemical structure stability, and is widely used as a material for enhancing mechanical properties; at the same time, due to the oxidation treatment, the surface of GO contains many active groups such as hydroxyl (-OH) and carboxyl (-COOH), making it have certain chemical reaction activity and capable of participating in reactions such as esterification and redox reactions and undergoing chemical transformation of functional groups. At present, many studies have reported using GO to enhance the mechanical properties of epoxy resins, but most studies are limited to the physical mixing and curing of GO and epoxy resins, and the chemical properties of GO have not been fully utilized to enhance the crosslinked network structure of epoxy resins. Therefore, establishing a molecular interface between GO and epoxy resin based on chemical methods, so as to fully exert the excellent mechanical properties of GO itself, has important application significance for strengthening the mechanical properties of epoxy resin modified asphalt. Summary of the Invention

[0004] The purpose of the present invention is to provide a graphene oxide composite epoxy resin modified asphalt and a preparation method thereof in order to solve the above problems.

[0005] The present invention realizes the above purpose through the following technical solutions:

[0006] The present invention provides a graphene oxide composite epoxy resin modified asphalt, and the preparation raw materials include TETA-GO, epoxy resin, and asphalt with a mass ratio of (0.75 - 1.5):10:100; wherein, the TETA-GO is obtained by introducing triethylenetetramine groups on the surface of graphene oxide.

[0007] As a further optimization scheme of the present invention, the preparation raw materials further include N-methylpyrrolidone, and the dosage of N-methylpyrrolidone is 1.2-2 times the mass of TETA-GO.

[0008] The present invention provides a preparation method of graphene oxide composite epoxy resin modified asphalt, comprising the following steps:

[0009] First, graphene oxide is ultrasonically dispersed in deionized water to obtain a graphene oxide dispersion; subsequently, it is added to a container together with triethylenetetramine and absolute ethanol, and stirred and mixed evenly at room temperature;

[0010] Second, nitrogen is filled into the container, and the container is sealed, and heated under a nitrogen atmosphere and certain temperature conditions to obtain a reaction product dispersion; after the reaction product dispersion is filtered and freeze-dried, the reaction product TETA-GO is obtained;

[0011] Third, after the reaction product TETA-GO is mixed with epoxy resin, it is added to the dried matrix asphalt, and shear dispersion is carried out at a certain temperature and rotation speed, and then kept static and developed for a certain time to obtain graphene oxide composite epoxy resin modified asphalt.

[0012] As a further optimization scheme of the present invention, in the first step, the mass ratio of the graphene oxide, deionized water, triethylenetetramine and absolute ethanol is (0.5-2.5):(40-100):(10-50):(40-100).

[0013] As a further optimization scheme of the present invention, in the first step, the ultrasonic dispersion time is 20 min-60 min, and the ultrasonic power is 200-1000 W; in the first step, the room temperature is 20°C-30°C, and the stirring time at room temperature is 1 h-3 h; the stirring speed is 200 r / min-800 r / min.

[0014] As a further optimization scheme of the present invention, in the second step, the temperature for maintaining heating is 80°C-100°C, and the heating time is 16 h-32 h.

[0015] As a further optimization scheme of the present invention, in the second step, the temperature for freeze-drying is -50°C--20°C, and the freeze-drying time is 4 h-8 h.

[0016] As a further optimization scheme of the present invention, in the third step, when the reaction product TETA-GO is mixed with epoxy resin, N-methylpyrrolidone is also added.

[0017] As a further optimized solution of the present invention, in step three, the shearing temperature is 155°C to 175°C, the shearing rate is 3000 r / min to 6000 r / min, and the shearing time is 30 min to 60 min; the heat preservation and static development temperature is 155°C to 175°C, and the development time is 90 min to 150 min.

[0018] The beneficial effects of the present invention are as follows:

[0019] 1) The graphene oxide composite epoxy resin modified asphalt prepared by the present invention has good anti-deformation performance. Compared with the control group of epoxy resin modified asphalt, the complex modulus is increased by 18.66% - 77.03% (46°C, 10 Hz), and the anti-deformation performance is increased by 18.66% - 77.03%, which can effectively improve the load-bearing capacity of the traditional epoxy resin modified asphalt pavement;

[0020] 2) The viscosity performance of the graphene oxide composite epoxy resin modified asphalt prepared by the present invention is improved, ensuring good adhesion effect of itself;

[0021] 3) The graphene oxide composite epoxy resin modified asphalt prepared by the present invention has good high-temperature rutting resistance. Compared with the control group of epoxy resin modified asphalt, the rutting factor is increased by 48.28% - 51.45% (76°C, 10 rad / s), which can effectively alleviate the occurrence of high-temperature rutting diseases on the traditional epoxy resin modified asphalt pavement;

[0022] 4) The present invention uses the combination of graphene oxide and triethylenetetramine (TETA). Compared with the combination of graphene oxide and diethylenetriamine (DETA), ethylenediamine (EDA), and tetraethylenepentamine (TEPA), it has a significant effect on improving the high-temperature rutting resistance of the graphene oxide composite epoxy resin modified asphalt. Description of the Drawings

[0023] Figure 1 It is the test result diagram of Fourier transform infrared spectroscopy (FT-IR) characterization of graphene oxide (GO), triethylenetetramine (TETA), and TETA-GO prepared in step two of Example 1 of the present invention (1 is TETA-GO, 2 is triethylenetetramine, and 3 is graphene oxide).

[0024] Figure 2The Fourier transform infrared spectroscopy (FT-IR) characterization test results of the TETA-GO prepared in Step 2 of Example 1 of the present invention, the uncured epoxy resin used in Step 3 of Example 1, and the graphene oxide composite epoxy resin obtained after elution of a graphene oxide composite epoxy modified asphalt are shown in the figure (1 is the graphene oxide composite epoxy resin obtained after elution, 2 is the uncured epoxy resin, and 3 is TETA-GO).

[0025] Figure 3 The fluorescence microscopy test results of the graphene oxide composite epoxy modified asphalt of Example 3 of the present invention and the epoxy modified asphalt of Comparative Example 3 are shown in the figure (a is the graphene oxide composite epoxy modified asphalt, and b is the control group epoxy modified asphalt).

[0026] Figure 4 The graph of the complex modulus of the graphene oxide composite epoxy modified asphalt (1) of Example 1 of the present invention and the epoxy modified asphalt (2) of Comparative Example 1 changing with temperature.

[0027] Figure 5 The graph of the phase angle of the graphene oxide composite epoxy modified asphalt (1) of Example 1 of the present invention and the epoxy modified asphalt (2) of Comparative Example 1 changing with temperature.

[0028] Figure 6 The graph of the complex modulus of the graphene oxide composite epoxy modified asphalt (1) of Example 2 of the present invention and the epoxy modified asphalt (2) of Comparative Example 2 changing with temperature.

[0029] Figure 7 The graph of the phase angle of the graphene oxide composite epoxy modified asphalt (1) of Example 2 of the present invention and the epoxy modified asphalt (2) of Comparative Example 2 changing with temperature.

[0030] Figure 8 The graph of the complex modulus of the graphene oxide composite epoxy modified asphalt (1) of Example 3 of the present invention and the epoxy modified asphalt (2) of Comparative Example 3 changing with temperature.

[0031] Figure 9 The graph of the phase angle of the graphene oxide composite epoxy modified asphalt (1) of Example 3 of the present invention and the epoxy modified asphalt (2) of Comparative Example 3 changing with temperature. Detailed implementation manners

[0032] The present application will be further described in detail below in conjunction with the accompanying drawings. It is necessary to point out here that the following specific embodiments are only used to further illustrate the present application and should not be construed as limiting the protection scope of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0033] I. Materials

[0034] 1. Graphene Oxide (GO), volume parameters: sheet diameter, 10 - 50 μm; thickness < 20 nm; specific surface area 100 - 300 m 2 / g; purchased from Suzhou Carbon Feng Electronic Technology Co., Ltd.

[0035] 2. Organic amine compounds: Triethylenetetramine (TETA), Diethylenetriamine (DETA), Ethylenediamine (EDA), Tetraethylenepentamine (TEPA), purchased from Shanghai Chuangsai Technology Co., Ltd.

[0036] 3. N-Methylpyrrolidone (NMP), Dimethylformamide (DMF), purchased from Shanghai Chuangsai Technology Co., Ltd.

[0037] The methods used in this application are all conventional methods known to those skilled in the art unless otherwise specified. The reagents and other materials used are all commercially available products unless otherwise specified.

[0038] II. Methods

[0039] Example 1

[0040] A preparation method of graphene oxide composite epoxy resin modified asphalt is as follows:

[0041] I. Add graphene oxide to deionized water and perform ultrasonic dispersion (20 min, 1000 W) to obtain a graphene oxide dispersion; then add it, together with triethylenetetramine and absolute ethanol, to a sealable container and initially stir at a rate of 200 r / min at room temperature of 20 °C for 3 h to mix evenly;

[0042] Among them, the mass ratio of graphene oxide, deionized water, triethylenetetramine and absolute ethanol is 0.5:40:10:40;

[0043] II. Fill the container with nitrogen, then seal the container, and keep heating at 80 °C under a nitrogen atmosphere for 30 h to obtain a reaction product dispersion; filter and freeze-dry the reaction product dispersion to obtain the reaction product TETA-GO;

[0044] III. After mixing TETA-GO with epoxy resin, add it to the dried matrix asphalt, and shear and disperse it for 60 min at a temperature of 155 °C and a rotation speed of 3000 r / min by a high-speed shear machine. Then, let the modified asphalt stand and develop at 155 °C for 150 min to finally obtain graphene oxide composite epoxy resin modified asphalt;

[0045] Among them, the mass ratio of TETA-GO, epoxy resin and matrix asphalt is 0.75:10:100.

[0046] Example 2

[0047] A preparation method of graphene oxide composite epoxy resin modified asphalt, the specific steps are as follows:

[0048] I. Add graphene oxide to deionized water and perform ultrasonic dispersion (40 min, 600 W) to obtain a graphene oxide dispersion; then add it, triethylenetetramine and absolute ethanol to a sealable container, and initially stir at a rate of 500 r / min at room temperature of 25 °C for 2 h to mix evenly;

[0049] Among them, the mass ratio of graphene oxide, deionized water, triethylenetetramine and absolute ethanol is 1.5:70:30:70;

[0050] II. Fill the container with nitrogen, then seal the container, and keep heating at 90 °C under a nitrogen atmosphere for 24 h to obtain a reaction product dispersion; filter and freeze-dry the reaction product dispersion to obtain the reaction product TETA-GO;

[0051] III. After mixing TETA-GO with epoxy resin, add it to the dried matrix asphalt, and perform shear dispersion at a temperature of 165 °C and a rotation speed of 4500 r / min by a high-speed shear machine for 45 min. Then, let the modified asphalt stand and develop at 165 °C for 120 min to finally obtain a graphene oxide composite epoxy resin modified asphalt;

[0052] Among them, the mass ratio of TETA-GO, epoxy resin and matrix asphalt is 1.125:10:100.

[0053] Example 3

[0054] A preparation method of graphene oxide composite epoxy resin modified asphalt, the specific steps are as follows:

[0055] I. Add graphene oxide to deionized water and perform ultrasonic dispersion (60 min, 200 W) to obtain a graphene oxide dispersion; then add it, triethylenetetramine and absolute ethanol to a sealable container, and initially stir at a rate of 200 r / min at room temperature of 30 °C for 1 h to mix evenly;

[0056] Among them, the mass ratio of graphene oxide, deionized water, triethylenetetramine and absolute ethanol is 2.5:100:50:100;

[0057] Second, fill the container with nitrogen, then seal the container, and keep heating for 16 h under the nitrogen atmosphere and at a temperature of 100 °C to obtain a reaction product dispersion; filter and freeze-dry the reaction product dispersion to obtain the reaction product TETA-GO;

[0058] Third, mix TETA-GO and epoxy resin, and then add them to the dried matrix asphalt. Shear and disperse them for 30 min at a temperature of 175 °C and a rotation speed of 6000 r / min by a high-speed shear machine. Then keep the modified asphalt standing and developing for 90 min at a temperature of 175 °C to finally obtain a graphene oxide composite epoxy resin modified asphalt;

[0059] Among them, the mass ratio of TETA-GO, epoxy resin and matrix asphalt is 1.5:10:100.

[0060] Example 4

[0061] A preparation method of a graphene oxide composite epoxy resin modified asphalt, the specific steps are as follows:

[0062] First, add graphene oxide to deionized water and perform ultrasonic dispersion (60 min, 200 W) to obtain a graphene oxide dispersion; then add it, triethylenetetramine and absolute ethanol to a sealable container, and initially stir at a rate of 200 r / min at room temperature of 30 °C for 1 h to mix evenly;

[0063] Among them, the mass ratio of graphene oxide, deionized water, triethylenetetramine and absolute ethanol is 2.5:100:50:100;

[0064] Second, fill the container with nitrogen, then seal the container, and keep heating for 16 h under the nitrogen atmosphere and at a temperature of 100 °C to obtain a reaction product dispersion; filter and freeze-dry the reaction product dispersion to obtain the reaction product TETA-GO;

[0065] Third, mix TETA-GO, epoxy resin and N-methylpyrrolidone (the dosage of N-methylpyrrolidone is 1.5 times the mass of TETA-GO), and then add them to the dried matrix asphalt. Shear and disperse them for 30 min at a temperature of 175 °C and a rotation speed of 6000 r / min by a high-speed shear machine. Then keep the modified asphalt standing and developing for 90 min at a temperature of 175 °C to finally obtain a graphene oxide composite epoxy resin modified asphalt;

[0066] Among them, the mass ratio of TETA-GO, epoxy resin and matrix asphalt is 1.5:10:100.

[0067] Comparative Example 1

[0068] The preparation method of epoxy resin modified asphalt is as follows:

[0069] After mixing TETA and epoxy resin, add them to the dried matrix asphalt, and carry out shear dispersion at a temperature of 155°C and a rotation speed of 3000 r / min by a high-speed shear machine for 60 min. Then, let the modified asphalt stand and develop at a temperature of 155°C for 150 min to finally obtain epoxy resin modified asphalt; among them, the mass ratio of TETA, epoxy resin and matrix asphalt is 0.5:10:100 (the same TETA content as in Example 1).

[0070] Comparative Example 2

[0071] The preparation method of epoxy resin modified asphalt is as follows:

[0072] After mixing TETA and epoxy resin, add them to the dried matrix asphalt, and carry out shear dispersion at a temperature of 165°C and a rotation speed of 4500 r / min by a high-speed shear machine for 45 min. Then, let the modified asphalt stand and develop at a temperature of 165°C for 120 min to finally obtain epoxy resin modified asphalt; among them, the mass ratio of TETA, epoxy resin and matrix asphalt is 0.75:10:100 (the same TETA content as in Example 2).

[0073] Comparative Example 3

[0074] The preparation method of epoxy resin modified asphalt is as follows:

[0075] After mixing TETA and epoxy resin, add them to the dried matrix asphalt, and carry out shear dispersion at a temperature of 175°C and a rotation speed of 6000 r / min by a high-speed shear machine for 30 min. Then, let the modified asphalt stand and develop at a temperature of 175°C for 90 min to finally obtain epoxy resin modified asphalt; among them, the mass ratio of TETA, epoxy resin and matrix asphalt is 1:10:100 (the same TETA content as in Example 3).

[0076] Comparative Example 4

[0077] Different from Example 3, in this comparative example, diethylenetriamine (DETA) with the same mass is used to replace triethylenetetramine (TETA), and the rest are the same as in Example 3.

[0078] Comparative Example 5

[0079] Different from Example 3, in this comparative example, ethylene diamine (EDA) with equal mass was used to replace triethylenetetramine (TETA), and the rest was the same as in Example 3.

[0080] Comparative Example 6

[0081] Different from Example 3, in this comparative example, tetraethylenepentamine (TEPA) with equal mass was used to replace triethylenetetramine (TETA), and the rest was the same as in Example 3.

[0082] Comparative Example 7

[0083] Different from Example 4, in this comparative example, dimethylformamide (DMF) with equal mass was used to replace N-methylpyrrolidone (NMP), and the rest was the same as in Example 4.

[0084] III. Tests

[0085] 3.1. Fourier transform infrared spectroscopy (FT-IR) characterizations were performed on graphene oxide, triethylenetetramine, and TETA-GO prepared in Step 2 of Example 1 respectively. The test results are as Figure 1 shown, where 1 is TETA-GO, 2 is triethylenetetramine, and 3 is graphene oxide.

[0086] From Figure 1It can be seen that GO contains an -OH stretching vibration absorption peak at 3621.6 cm-1, a C=O stretching vibration absorption peak at 1733.6 cm-1, an -OH bending vibration absorption peak at 1400.3 cm-1, a C=C stretching vibration absorption peak at 1623.7 cm-1, a C-O-C stretching vibration absorption peak at 1253.6 cm-1, and a C-O stretching vibration absorption peak at 1043.2 cm-1, indicating that its surface contains carboxyl (-COOH) and epoxy groups. For TETA, it contains N-H stretching vibration absorption peaks at 3357.5 cm-1 and 3276.4 cm-1, N-H bending vibration absorption peaks at 1589.0 cm-1 and 1455.9 cm-1, and C-H stretching vibration absorption peaks at 2927.4 cm-1 and 2803.9 cm-1, indicating that its chemical structure contains amino (-NH2), imino (-N-H), methyl (-CH3-), and methylene (-CH2-). When TETA is grafted onto the surface of GO, N-H stretching vibration absorption peaks at 3345.8 cm-1 and 3239.8 cm-1, N-H bending vibration absorption peaks at 1558.2 cm-1 and 1471.4 cm-1, and C-H stretching vibration absorption peaks at 2942.8 cm-1 and 2840.6 cm-1, which originally belonged to TETA, appear in its infrared spectrum, indicating that TETA has been grafted onto the surface of GO; at the same time, the C=O stretching vibration absorption peak at 1733.6 cm-1, the C-O-C stretching vibration absorption peak at 1253.6 cm-1, and the C-O stretching vibration absorption peak at 1043.2 cm-1 disappear, indicating a decrease in the content of -COOH and epoxy groups on the surface of GO, suggesting that the grafting process of TETA is achieved by covalent bonding with -COOH and epoxy groups on the surface of GO. Different TETA-GOs obtained through Examples 1, 2, and 3 show the same absorption peaks in the FT-IR test results, and the difference lies in the intensity of the absorption peaks, so they are not shown here.

[0087] 3.2 Fourier transform infrared spectroscopy (FT-IR) characterization tests were respectively carried out on the TETA-GO prepared in Step 2 of Example 1, the uncured epoxy resin used in Step 3 of Example 1, and the graphene oxide composite epoxy resin obtained after elution of a graphene oxide composite epoxy asphalt. The test results are as Figure 2 shown, where 1 is the graphene oxide composite epoxy resin obtained after elution, 2 is the uncured epoxy resin, and 3 is TETA-GO.

[0088] From Figure 2It can be seen that the uncured epoxy resin contains a C-O-C stretching vibration absorption peak at 1238.1 cm-1, a C-O stretching vibration absorption peak at 1043.2 cm-1, and a C-O-C stretching vibration absorption peak at 912.7 cm-1, which represent the epoxy groups contained in its chemical structure. By comparing with the infrared spectra of the epoxy resin composite with TETA-GO and the graphene oxide obtained after elution, it can be found that the intensities of the three infrared absorption peaks decrease significantly, indicating that the curing reaction consumes the epoxy groups in the epoxy resin and realizes the ring-opening curing process.

[0089] 3.3. Fluorescence microscopy tests were carried out on the graphene oxide composite epoxy resin modified asphalt obtained in Example 3 and the epoxy resin modified asphalt obtained in Comparative Example 3. The test results are as Figure 3 shown, where a is the graphene oxide composite epoxy resin modified asphalt and b is the control group epoxy resin modified asphalt.

[0090] It is considered that the high strength of the epoxy resin modified asphalt is due to the thermosetting resin formed by its curing in the asphalt, which can form a plastic skeleton structure in the asphalt and thus play a supporting role. However, the size of the particles has a great influence on the supporting effect. From Figure 3 it can be seen that the resin particles formed in the control group epoxy resin modified asphalt are generally small in volume and relatively concentrated in dispersion, so the supporting effect should be weak; the resin particles formed in the graphene oxide composite epoxy resin modified asphalt are generally large in volume and relatively dispersed in dispersion, so the supporting effect should be strong. The different graphene oxide composite epoxy resin modified asphalts obtained through Examples 1, 2, and 3 show similar resin particles in the fluorescence microscopy test results. The difference lies in the particle size and density, so they are not shown here.

[0091] 3.4. Through dynamic shear rheological tests, the curves of the complex modulus of the graphene oxide composite epoxy resin modified asphalts obtained in Examples 1-3 of the present invention and the epoxy resin modified asphalts obtained in Comparative Examples 1-3 changing with temperature ( Figure 4 , taking the test frequency of 10 Hz and the test temperature of 46 °C - 82 °C as an example), the curves of the phase angle changing with temperature ( Figure 5 , taking the test frequency of 10 Hz and the test temperature of 46 °C - 82 °C as an example), and the change of the rutting factor of the modified asphalts in Examples 1-3 and Comparative Examples 1-6 with temperature after short-term aging (Table 1, taking the test frequency of 10 rad / s and the test temperature of 64 °C - 82 °C as an example) were respectively detected, where Figure 4-5 in, 1 is the graphene oxide composite epoxy resin modified asphalt obtained in Example 1, and 2 is the epoxy resin modified asphalt obtained in Comparative Example 1; Figure 6-7Among them, 1 is the graphene oxide composite epoxy resin modified asphalt obtained in Example 2, and 2 is the epoxy resin modified asphalt obtained in Comparative Example 2; Figure 8-9 Among them, 1 is the graphene oxide composite epoxy resin modified asphalt obtained in Example 3, and 2 is the epoxy resin modified asphalt obtained in Comparative Example 3.

[0092] Table 1 Rutting factors of the modified asphalts of Examples 1 - 3 and Comparative Examples 1 - 6 at various temperatures

[0093]

[0094] Variation of the rutting factor with temperature of the modified asphalts of Example 4 and Comparative Example 7 after short - term aging (Table 2, taking a test frequency of 10 rad / s and test temperatures from 64°C to 82°C as an example):

[0095] Table 2 Rutting factors of the modified asphalts of Example 4 and Comparative Example 7 at various temperatures

[0096]

[0097]

[0098] Note: The complex modulus represents the anti - deformation performance of asphalt. The larger the value, the stronger the anti - deformation performance; the phase angle represents the proportion of the visco - elastic property of asphalt. The larger the phase angle value, the greater the proportion of the viscous property; the rutting factor represents the anti - rutting performance of asphalt. The larger the value, the stronger the performance.

[0099] From Figure 4 it can be seen that at the same test frequency (10 Hz), the complex modulus of all asphalts decreases with the increase of the test temperature; the value of the graphene oxide composite epoxy resin modified asphalt is always greater than that of the control group epoxy resin modified asphalt, with a 18.66% increase (at 46°C) compared to the latter, proving that the anti - deformation performance of the modified asphalt obtained by the present invention is improved. From Figure 5 it can be seen that at the same test frequency (10 Hz), the phase angle of all asphalts increases with the increase of the test temperature; the value of the graphene oxide composite epoxy resin modified asphalt is always greater than that of the control group epoxy resin modified asphalt; proving that the proportion of the viscous property of the modified asphalt obtained by the present invention increases and the viscous property is enhanced. As can be seen from Table 1, the rutting factors of the modified asphalts all show a significant increase after short - term aging treatment, but the change amount gradually decreases with the increase of temperature; among them, the change amount of the graphene oxide composite epoxy resin modified asphalt is always greater than that of the control group epoxy resin modified asphalt, with a 48.28% increase (at 76°C) compared to the latter, proving that the anti - rutting performance of the modified asphalt obtained by the present invention is improved.

[0100] From Figure 6It can be seen that at the same test frequency (10 Hz), the complex modulus of all bitumens decreases with the increase of the test temperature; the value of the graphene oxide composite epoxy resin modified bitumen is always greater than that of the control group epoxy resin modified bitumen, and it is increased by 61.57% (at 46 °C) compared with the latter, indicating that the modified bitumen obtained by the present invention has improved anti-deformation performance. From Figure 7 It can be seen that at the same test frequency (10 Hz), the phase angle of all bitumens increases with the increase of the test temperature; the value of the graphene oxide composite epoxy resin modified bitumen is always greater than that of the control group epoxy resin modified bitumen, proving that the proportion of the viscous property of the modified bitumen obtained by the present invention increases and the viscous property is enhanced. As can be seen from Table 2, the rutting factors of the modified bitumens all show obvious improvement after short-term aging treatment, but the change amount gradually decreases with the increase of the temperature; among them, the change amount of the graphene oxide composite epoxy resin modified bitumen is always greater than that of the control group epoxy resin modified bitumen, and it is increased by 51.34% (at 76 °C) compared with the latter, indicating that the modified bitumen obtained by the present invention has improved rutting resistance.

[0101] From Figure 8 It can be seen that at the same test frequency (10 Hz), the complex modulus of all bitumens decreases with the increase of the test temperature; the value of the graphene oxide composite epoxy resin modified bitumen is always greater than that of the control group epoxy resin modified bitumen, and it is increased by 77.03% (at 46 °C) compared with the latter, indicating that the modified bitumen obtained by the present invention has improved anti-deformation performance. From Figure 9 It can be seen that at the same test frequency (10 Hz), the phase angle of all bitumens increases with the increase of the test temperature; the value of the graphene oxide composite epoxy resin modified bitumen is always greater than that of the control group epoxy resin modified bitumen, proving that the proportion of the viscous property of the modified bitumen obtained by the present invention increases and the viscous property is enhanced. As can be seen from Table 1, the rutting factors of the modified bitumens all show obvious improvement after short-term aging treatment, but the change amount gradually decreases with the increase of the temperature; among them, the change amount of the graphene oxide composite epoxy resin modified bitumen is always greater than that of the control group epoxy resin modified bitumen, and it is increased by 51.26% (at 76 °C) compared with the latter, indicating that the modified bitumen obtained by the present invention has improved rutting resistance.

[0102] It can be known from Table 2 that when TETA-GO is mixed with epoxy resin, adding N-methylpyrrolidone will make the rutting factor of the modified bitumen higher under the temperature conditions of 70 °C - 82 °C after short-term aging treatment, but replacing N-methylpyrrolidone with dimethylformamide (DMF) cannot achieve this effect, indicating that N-methylpyrrolidone has a specific effect in this system.

[0103] The above-described embodiments merely represent several implementation manners of the present invention. The description thereof is relatively specific and detailed, but it should not be construed as a limitation to the scope of the patent of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all fall within the protection scope of the present invention.

Claims

1. A graphene oxide composite epoxy resin modified asphalt, characterized in that: The preparation raw materials include TETA-GO, epoxy resin and asphalt in a mass ratio of (0.75-1.5):10:100; wherein the TETA-GO is obtained by introducing triethyltetramine groups on the surface of graphene oxide.

2. The graphene oxide composite epoxy resin modified asphalt according to claim 1, characterized in that: The preparation raw materials also include N-methylpyrrolidone, and the amount of N-methylpyrrolidone is 1.2-2 times the mass of TETA-GO.

3. A method for preparing graphene oxide composite epoxy resin modified asphalt as described in any one of claims 1-2, characterized in that: The following steps are involved:

1. Ultrasonic dispersion of graphene oxide in deionized water to obtain graphene oxide dispersion; then adding graphene oxide dispersion, triethylenetetramine and anhydrous ethanol into a container, and stirring and mixing at room temperature; 2. Filling nitrogen into the container, sealing the container, and heating it under nitrogen atmosphere and certain temperature conditions to obtain a dispersion of the reaction product; filtering and freeze-drying the dispersion of the reaction product to obtain the reaction product TETA-GO; 3. After mixing the reaction product TETA-GO with epoxy resin, add it to the dried matrix asphalt, shear and disperse it at a certain temperature and speed, and then keep it warm and static for a certain period of time to obtain graphene oxide composite epoxy resin modified asphalt.

4. The method for preparing a graphene oxide composite epoxy resin modified asphalt according to claim 3, characterized in that: In step 1, the mass ratio of graphene oxide, deionized water, triethylenetetramine and anhydrous ethanol is (0.5-2.5):(40-100):(10-50):(40-100).

5. The method for preparing a graphene oxide composite epoxy resin modified asphalt according to claim 3, characterized in that: In step one, the ultrasonic dispersion time is 20 min to 60 min, and the ultrasonic power is 200 to 1000 W; in step one, the room temperature is 20°C to 30°C, and the stirring time at room temperature is 1 h to 3 h; the stirring speed is 200 r / min to 800 r / min; in step one, the mass ratio of TETA-GO, epoxy resin and matrix asphalt is (0.75 to 1.5):10:

100.

6. The method for preparing a graphene oxide composite epoxy resin modified asphalt according to claim 3, characterized in that: In step 2, the heating temperature is maintained at 80° C. to 100° C., and the heating time is 16 h to 32 h.

7. The method for preparing a graphene oxide composite epoxy resin modified asphalt according to claim 3, characterized in that: In step 2, the freeze-drying temperature is -50°C to -20°C, and the freeze-drying time is 4h to 8h.

8. The method for preparing a graphene oxide composite epoxy resin modified asphalt according to claim 3, characterized in that: In step three, when the reaction product TETA-GO is mixed with epoxy resin, N-methylpyrrolidone is also added.

9. The method for preparing a graphene oxide composite epoxy resin modified asphalt according to claim 3, characterized in that: In step three, the shear temperature is 155°C to 175°C, the shear rate is 3000r / min to 6000r / min, and the shear time is 30min to 60min; the heat preservation static development temperature is 155°C to 175°C, and the development time is 90min to 150min.

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