IRMOF-1-NH2 / SBS composite modifier as well as preparation method and application thereof

Abstract

The invention discloses an IRMOF-1-NH2 / SBS composite modifier as well as a preparation method and application thereof, and belongs to the technical field of asphalt processing. The composite modifier is prepared from the following raw materials in percentage by mass: 28 percent to 35 percent of IRMOF-1-NH2, 53 percent to 61 percent of SBS (Styrene Butadiene Styrene), 0.2 percent to 0.4 percent of an accelerant and 10.6 percent to 14.6 percent of a compatilizer; the preparation method of the IRMOF-1-NH2 comprises the following steps: S1, adding soluble zinc salt and 2-aminoterephthalic acid into a solvent, carrying out ultrasonic treatment, reacting at 120-150 DEG C for 12-24 hours, and separating and washing to obtain a solid product; and S2, heating the solid product obtained in the step S1 at the temperature of 100-150 DEG C for 10-20 hours to obtain the IRMOF-1-NH2 crystal. The compound modifier disclosed by the invention can be used for efficiently storing aromatics, so that the effect of inhibiting the aromatics from being gelatinized is achieved, and the anti-aging performance of asphalt is remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of asphalt processing, and particularly relates to an IRMOF-1-NH 2 / SBS composite modifier, its preparation method and application. Background Art

[0002] The high and low temperature performance of ordinary asphalt is poor. The pavement paved with it is prone to diseases such as ruts and potholes, and has a short service life. Especially under heavy traffic conditions, it is extremely easy to be damaged. To solve this problem, polymers are usually used to modify asphalt, so as to improve the road performance of asphalt mixtures. Among them, styrene-butadiene-styrene triblock copolymer (SBS) can significantly improve the high temperature rutting resistance and low temperature cracking resistance of asphalt by forming a network structure in asphalt through physical crosslinking. SBS modified asphalt pavement has become the most widely used modified asphalt in the world. However, during the long-term use of SBS modified asphalt pavement, due to the influence of natural factors such as heat, moisture, ultraviolet rays, and oxygen and the action of vehicle loads, many complex physical and chemical changes will occur, resulting in the aging and degradation of SBS modified asphalt and the deterioration of asphalt performance. Eventually, pavement diseases such as ruts, spalling, cracks, and potholes will appear on the pavement, seriously affecting the durability of asphalt pavement. Whether it is thermal-oxidative aging or ultraviolet aging of asphalt, it will cause the following changes in the components and structure of asphalt: aromatic fraction → resin → asphaltene. Specifically, the aromatic fraction and resin will react, so that their contents continuously decrease, making the original colloidal structure of asphalt gradually gelate, thereby reducing the use performance of asphalt (such as increased viscosity, decreased ductility and adhesion, etc.), and finally seriously shortening the service life of asphalt pavement. It can be seen that retaining the aromatic components in asphalt and inhibiting the gelation of asphalt structure are the keys to improving the anti-aging performance of asphalt.

[0003] MOF materials are crystalline porous materials formed by the self-assembly of metal ions and organic ligands. They have characteristics such as high specific surface area, high porosity, and adjustable pore size, which are beneficial for gas storage and separation. In addition, the pore size and shape of MOF can be controlled by adjusting the structure and length of the ligand, thereby achieving selective adsorption of different molecules. Among them, IRMOF-1 is a well-known zinc-based metal-organic framework (Zn-MOF) material, which has excellent stability, good tolerance in synthesis, and excellent gas storage capacity, and has attracted much attention especially in the field of capturing benzene series (aromatic components). At present, some studies have proposed to use metal-organic framework materials to delay the aging of matrix asphalt. For example, Chinese Patent CN116444815A discloses a hybrid coordination polymerization type metal-organic framework anti-aging agent, modified asphalt and its preparation method. This patent mixes three metal-organic framework materials with different pores, specific surface areas, and metal sites, and uses the synergistic effect of multiple MOFs materials to adsorb various aging components in asphalt, hindering the oxidative aging of asphalt and achieving an anti-aging effect. However, the anti-aging effect of using metal-organic frameworks alone is limited, and this anti-aging agent does not contain polar groups and cannot form hydrogen bonds with the π electron cloud on the benzene ring to produce H-π interaction, so its adsorption capacity for benzene is limited, and the effect of improving the anti-aging performance of asphalt is limited, which restricts its application in asphalt.

[0004] Therefore, it is proposed to explore new ideas for asphalt anti-aging, and it is of great significance to design and prepare a new type of metal-organic framework compound material for storing aromatic components and use it to improve the performance of SBS modified asphalt. Summary of the Invention

[0005] Aiming at the above deficiencies of the prior art, one of the purposes of the present invention is to provide an IRMOF-1-NH 2 / SBS composite modifier. On the one hand, due to the presence of organic ligands in the structure of IRMOF-1-NH 2 , the affinity between IRMOF-1-NH 2 material and SBS particles can be enhanced, so that the two have good compatibility and stability. On the other hand, the IRMOF-1-NH 2 material can design and regulate pore characteristics and surface chemical characteristics by adjusting metal ions and organic ligands. When benzene series are volatilized during the aging process of asphalt, IRMOF-1-NH 2 can efficiently store them, and finally achieve the purpose of storing aromatic components. In addition, the introduced IRMOF-1-NH 2 has a benzene ring and has the ability to absorb ultraviolet light.

[0006] The above object of the present invention is achieved by the following technical solutions:

[0007] An IRMOF-1-NH 2 / SBS composite modifier, by mass fraction, comprises the following raw materials: IRMOF-1-NH 2 28% - 35%, SBS 53% - 61%, accelerator 0.2% - 0.4%, compatibilizer 10.6% - 14.6%;

[0008] The preparation method of the said IRMOF-1-NH 2 comprises the following steps:

[0009] S1. Add soluble zinc salt and 2-aminoterephthalic acid into a solvent, perform ultrasonic treatment, and then react at 100 - 150 °C for 12 - 24 h. After separation and washing, a solid product is obtained;

[0010] S2. Heat the solid product obtained in step S1 at 100 - 150 °C for 10 - 20 h to obtain IRMOF-1-NH 2 crystals.

[0011] In the composite modifier of the present invention, IRMOF-1-NH 2 can efficiently store aromatic components during the asphalt aging process, thereby inhibiting the gelation of the asphalt structure and enhancing the anti-aging performance of the asphalt. In addition, IRMOF-1-NH 2 has good compatibility with SBS. IRMOF-1-NH 2 can cooperate with SBS to enhance the modification effect of the composite modifier and significantly improve the anti-aging performance of the asphalt. Further, by performing amino-functionalization on IRMOF-1, on the one hand, the hydrogen atoms of the amino groups in IRMOF-1-NH 2 can act as hydrogen bond donors, form hydrogen bonds with the π electron clouds on the benzene ring, enhance the H-π interaction, and improve the adsorption capacity of the composite modifier for benzene series substances; on the other hand, the amino group is a polar group, which can enhance the polarity of the composite modifier and improve its adsorption capacity for benzene series substances; thus, it can efficiently store aromatic components and effectively improve the anti-aging performance of the asphalt.

[0012] Preferably, by mass fraction, the composite modifier comprises the following raw materials: IRMOF-1-NH 2 32%, SBS 53%, accelerator 0.4%, compatibilizer 14.6%.

[0013] Preferably, the mass ratio of the soluble zinc salt to 2-aminoterephthalic acid is (3 - 4.5):1. More preferably, the mass ratio of the soluble zinc salt to 2-aminoterephthalic acid is 3.5:1.

[0014] Preferably, in step S1, the soluble zinc salt is at least one of zinc chloride, zinc nitrate, and zinc acetate; and / or, the concentration of the soluble zinc salt in the solvent is 2%wt to 5%wt.

[0015] Preferably, in step S1, the solvent is at least one of N,N-dimethylformamide, γ-valerolactone (GVL), N,N-diethylformamide (DEF), and ethanol.

[0016] Preferably, the accelerator is at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and bis(1,5-pentamethylene)tetramthiuram tetrasulfide; the compatibilizer is catalytic slurry.

[0017] Another object of the present invention is to provide a preparation method of the IRMOF-1-NH 2 / SBS composite modifier, comprising the following steps:

[0018] P1. Prepare the IRMOF-1-NH 2 , SBS, accelerator, and compatibilizer according to their respective mass fractions, and then place them in a mixer for blending. The blending temperature is 90~100°C, and the speed is 1300~1500 r / min to obtain a blend;

[0019] P2. Add the blend obtained in step P1 to a granulator to granulate to obtain the IRMOF-1-NH 2 / SBS composite modifier.

[0020] Using the IRMOF-1-NH 2 / SBS composite modifier to prepare aging-resistant SBS modified asphalt, the obtained aging-resistant IRMOF-1-NH 2 / SBS modified asphalt comprises the following raw materials with the following mass fractions: asphalt 89.5%~93.5%, IRMOF-1-NH 2 / SBS composite modifier 6%~10%, stabilizer 0.1%~1.0%.

[0021] Preferably, the stabilizer is sulfur.

[0022] The present invention also provides a preparation method of the aging-resistant IRMOF-1-NH 2 / SBS modified asphalt, comprising the following steps: Prepare the asphalt, IRMOF-1-NH 2 / SBS composite modifier, and stabilizer according to their respective mass fractions; then heat the asphalt to a flowing state, and slowly add the IRMOF-1-NH 2 / SBS composite modifier and stabilizer, maintain the temperature at 160 - 180 °C, stir at a speed of 4000 - 6000 rpm for 1 - 3 h, and then continue to stir at a speed of 400 - 600 rpm for 1 - 3 h to obtain the anti-aging IRMOF-1-NH 2 / SBS modified asphalt.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] (1) In the composite modifier of the present invention, IRMOF-1-NH 2 can design and regulate pore characteristics and surface chemical characteristics by adjusting metal ions and organic ligands. When benzene series substances volatilize during the aging process of asphalt, IRMOF-1-NH 2 can efficiently store these aromatic components, thereby achieving the effect of inhibiting its gelation, and further effectively improving the anti-aging performance of asphalt. In addition, in the present invention, IRMOF-1-NH 2 is obtained by amino-functionalizing IRMOF-1, which can significantly improve the adsorption capacity of the composite modifier for benzene series substances, thereby efficiently storing aromatic components and effectively improving the anti-aging performance of asphalt.

[0025] (2) IRMOF-1-NH in the composite modifier of the present invention 2 has a benzene ring and has the ability to absorb ultraviolet light. In addition, the introduced benzene ring structure in IRMOF-1-NH 2 can cooperate with the benzene ring in the stored aromatic components to jointly absorb ultraviolet light, effectively inhibiting the damage of ultraviolet light to asphalt, thereby enhancing the anti-ultraviolet aging performance of asphalt.

[0026] (3) The presence of the organic ligand in the structure of IRMOF-1-NH in the composite modifier of the present invention 2 can enhance the affinity between the MOF material and SBS particles, so that the two have good compatibility and stability. IRMOF-1-NH 2 can cooperate with SBS to improve the modification effect of the composite modifier, significantly enhancing the anti-aging performance of asphalt. Detailed implementation manners

[0027] The technical solutions of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0028] The embodiment of the present invention provides an IRMOF-1-NH 2 / SBS composite modifier, calculated by mass fraction, includes the following raw materials: IRMOF-1-NH 2 28%~35%, SBS 53%~61%, accelerator 0.2%~0.4%, compatibilizer 10.6%~14.6%;

[0029] The IRMOF-1-NH 2 The preparation method comprises the following steps:

[0030] S1. Add soluble zinc salt and 2-aminoterephthalic acid into a solvent, perform ultrasonic treatment, react at 100-150° C. for 12-24 hours, and obtain a solid product after separation and washing;

[0031] S2, heating the solid product obtained in step S1 at 100-150°C for 10-20h to obtain IRMOF-1-NH 2 Crystal.

[0032] Wherein, the mass ratio of the soluble zinc salt to 2-aminoterephthalic acid is (3-4.5):1.

[0033] The soluble zinc salt is at least one of zinc chloride, zinc nitrate and zinc acetate; the concentration of the soluble zinc salt in the solvent is 2%wt~5%wt.

[0034] The solvent may be at least one of N,N-dimethylformamide, γ-valerolactone (GVL), N,N-diethylformamide (DEF), and ethanol.

[0035] The accelerator is at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and bis(1,5-pentylene)thiuram tetrasulfide.

[0036] In the following examples and comparative examples, zinc nitrate hexahydrate was purchased from Xilong Chemical Co., Ltd., SBS was purchased from Hunan Yueyang Baling Petrochemical Co., Ltd., dichloromethane and N,N-dimethylformamide were purchased from Shanghai MacLean Biochemical Technology Co., Ltd., 2-aminoterephthalic acid was purchased from Shanghai Haohong Biomedical Technology Co., Ltd., tetramethylthiuram disulfide was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., and catalytic slurry was purchased from Changqing Oilfield Branch of China National Petroleum Corporation; all raw materials are common raw materials on the market. Unless otherwise specified, the density of the catalytic slurry at 20°C in the following examples and comparative examples is 900~1100kg / m 3 , 40°C kinematic viscosity is 400~550mm 2 / s; the asphalt is road petroleum asphalt, with a needle penetration of 60~120dmm at 25°C, a softening point of 40~55°C, and an elongation of 15~25cm at 10°C.

[0037] Example 1

[0038] This example provides an IRMOF-1-NH 2 / SBS composite modifier, which consists of the following raw materials by mass fraction: 32.00% IRMOF-1-NH 2 , 53.00% SBS, 0.40% tetramethylthiuram disulfide, 14.60% catalytic slurry;

[0039] Among them, the preparation method of IRMOF-1-NH 2 includes the following steps:

[0040] S1. Mix zinc nitrate hexahydrate, 2-aminoterephthalic acid, and N,N-dimethylformamide in a mass ratio of 3.5:1:100, ultrasonically dissolve them, and then load them into a polytetrafluoroethylene reaction kettle;

[0041] S2. React in an oven at 120°C for 12 h, and centrifuge to collect the precipitate;

[0042] S3. Wash the product 3 times with N,N-dimethylformamide and dichloromethane respectively and centrifuge to collect;

[0043] S4. Place the product in an oven at 120°C and dry it for 12 h to obtain the metal-organic framework IRMOF-1-NH 2 crystals.

[0044] The preparation method of the IRMOF-1-NH 2 / SBS composite modifier in this example includes the following steps:

[0045] P1. Place IRMOF-1-NH 2 , SBS, tetramethylthiuram disulfide, and catalytic slurry in a high-speed mixer (model: SHR-5A) for blending. The blending temperature is 95°C, the speed is 1300 r / min, and the time is 8 min to obtain a mixture;

[0046] P2. Add the mixture obtained after blending in step P1 to a single-screw granulator and extrude and granulate. The head temperature is 165°C to obtain the IRMOF-1-NH 2 / SBS composite modifier.

[0047] The above IRMOF-1-NH 2 / SBS composite modifier is used to prepare aging-resistant IRMOF-1-NH 2 / SBS modified asphalt, and the aging-resistant IRMOF-1-NH 2 / SBS modified asphalt, by mass fraction, consists of the following raw materials: asphalt 92.00%, IRMOF-1-NH 2 / SBS composite modifier 7.50%, sulfur 0.50%;

[0048] The preparation method of the anti-aging IRMOF-1-NH 2 / SBS modified asphalt is as follows:

[0049] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and slowly add IRMOF-1-NH 2 / SBS composite modifier and sulfur, keep the temperature at 165 °C, start the high-speed shearer, and stir at a speed of 5000 rpm for 1.5 h; continue to keep 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the anti-aging IRMOF-1-NH 2 / SBS modified asphalt.

[0050] Example 2

[0051] The IRMOF-1-NH 2 / SBS composite modifier provided in this example, by mass fraction, consists of the following raw materials: 35.00% IRMOF-1-NH 2 , 54.00% SBS, 0.20% tetramethylthiuram disulfide, 10.80% catalytic slurry;

[0052] Among them, the preparation method of IRMOF-1-NH 2 is the same as that in Example 1;

[0053] The preparation method of the IRMOF-1-NH 2 / SBS composite modifier is the same as that in Example 1;

[0054] Use the above IRMOF-1-NH2 / SBS composite modifier to prepare anti-aging IRMOF-1-NH 2 / SBS modified asphalt. The anti-aging IRMOF-1-NH2 / SBS modified asphalt, by mass fraction, consists of the following raw materials: asphalt 93.00%, IRMOF-1-NH 2 / SBS composite modifier 6.50%, sulfur 0.50%;

[0055] The preparation method of the anti-aging IRMOF-1-NH2 / SBS modified asphalt is the same as that in Example 1.

[0056] Example 3

[0057] The IRMOF-1-NH 2 / SBS composite modifier, by mass fraction, consists of the following raw materials: 28.00% IRMOF-1-NH 2 , 61.00% SBS, 0.40% tetramethylthiuram disulfide, 10.60% catalytic slurry;

[0058] Among them, the preparation method of IRMOF-1-NH 2 is the same as that in Example 1;

[0059] The preparation method of the IRMOF-1-NH 2 / SBS composite modifier is the same as that in Example 1;

[0060] The above-mentioned IRMOF-1-NH 2 / SBS composite modifier is used to prepare aging-resistant IRMOF-1-NH 2 / SBS modified asphalt. The aging-resistant IRMOF-1-NH 2 / SBS modified asphalt, by mass fraction, consists of the following raw materials: 90.00% asphalt, IRMOF-1-NH 2 / SBS composite modifier 9.50%, sulfur 0.50%;

[0061] The preparation method of the aging-resistant IRMOF-1-NH 2 / SBS modified asphalt is the same as that in Example 1.

[0062] Example 4

[0063] The IRMOF-1-NH 2 / SBS composite modifier in this example is basically the same as that in Example 1, except that in step S1, the mass ratio of zinc nitrate hexahydrate, 2-aminoterephthalic acid, and N,N-dimethylformamide is 3:1:100.

[0064] Example 5

[0065] The IRMOF-1-NH 2 / SBS composite modifier in this example is basically the same as that in Example 1, except that in step S1, the mass ratio of zinc nitrate hexahydrate, 2-aminoterephthalic acid, and N,N-dimethylformamide is 4.5:1:100.

[0066] Comparative Example 1

[0067] The composite modifier in this comparative example, by mass fraction, consists of the following raw materials: 85.00% SBS, 0.40% tetramethylthiuram disulfide, 14.60% catalytic slurry;

[0068] The preparation method of the SBS composite modifier in this comparative example includes the following steps:

[0069] P1. Place SBS, tetramethylthiuram disulfide, and catalytic slurry into a high-speed mixer (model: SHR-5A) for blending. The blending temperature is 95°C, the speed is 1300 r / min, and the time is 8 min to obtain a mixture.

[0070] P2. Add the mixture obtained in step P1 to a single-screw granulator for extrusion granulation. The head temperature is 165°C to obtain an SBS composite modifier.

[0071] Use the above SBS composite modifier to prepare aging-resistant SBS modified asphalt. The aging-resistant SBS modified asphalt is composed of the following raw materials by mass fraction: 92.00% asphalt, 7.50% SBS composite modifier, and 0.50% sulfur.

[0072] The preparation method of the aging-resistant SBS modified asphalt is as follows:

[0073] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and simultaneously slowly add the SBS composite modifier and sulfur. Keep the temperature at 165°C, start the high-speed shear mixer, and stir at a speed of 5000 rpm for 1.5 h; continue to keep the temperature at 165°C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the aging-resistant SBS modified asphalt.

[0074] That is, compared with Example 1, the composite modifier in this comparative example does not contain IRMOF-1-NH 2 .

[0075] Comparative Example 2

[0076] The IRMOF-1-NH 2 composite modifier in this comparative example is composed of the following raw materials by mass fraction: 85.00% IRMOF-1-NH 2 , 0.40% tetramethylthiuram disulfide, and 14.60% catalytic slurry;

[0077] Among them, the preparation method of IRMOF-1-NH 2 is the same as that in Example 1;

[0078] The preparation method of the IRMOF-1-NH 2 composite modifier in this comparative example includes the following steps:

[0079] P1. Place IRMOF-1-NH 2 , tetramethylthiuram disulfide, and catalytic slurry into a high-speed mixer (model: SHR-5A) for blending. The blending temperature is 95°C, the speed is 1300 r / min, and the time is 8 min to obtain a mixture;

[0080] P2. Add the mixture obtained in step P1 to a single-screw granulator and extrude and granulate it. The head temperature is 165 °C to obtain IRMOF-1-NH 2 composite modifier.

[0081] Use the above IRMOF-1-NH 2 composite modifier to prepare aging-resistant IRMOF-1-NH 2 modified asphalt. The aging-resistant IRMOF-1-NH 2 modified asphalt is composed of the following raw materials by mass fraction: asphalt 92.00%, IRMOF-1-NH 2 composite modifier 7.50%, sulfur 0.50%;

[0082] The preparation method of the aging-resistant IRMOF-1-NH 2 modified asphalt is as follows:

[0083] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and slowly add IRMOF-1-NH 2 composite modifier and sulfur, keep the temperature at 165 °C, start the high-speed shearer, and stir at a speed of 5000 rpm for 1.5 h; continue to keep 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain aging-resistant IRMOF-1-NH 2 modified asphalt.

[0084] That is, compared with Example 1, the composite modifier in this comparative example does not contain SBS.

[0085] Comparative Example 3

[0086] The composite modifier in this comparative example is basically the same as that in Comparative Example 2, and the difference is only that IRMOF-1 is used to replace IRMOF-1-NH 2 ;

[0087] The preparation method of IRMOF-1 includes the following steps:

[0088] S1. Mix zinc nitrate hexahydrate, terephthalic acid, and N,N-dimethylformamide in a mass ratio of 3.5:1:100, ultrasonically dissolve them, and then load them into a polytetrafluoroethylene reaction kettle;

[0089] S2. React in an oven at 120 °C for 12 h, and centrifuge to collect the precipitate;

[0090] S3. Wash the product 3 times with N,N-dimethylformamide and dichloromethane respectively and centrifuge to collect;

[0091] S4. Place the product in an oven at 120 °C and dry it for 12 h to obtain metal-organic framework IRMOF-1 crystals.

[0092] That is, compared with Comparative Example 2, IRMOF-1 is not subjected to amino functionalization in this comparative example.

[0093] Comparative Example 4

[0094] The IRMOF-1-NH 2 / SBS composite modifier and its preparation method are the same as those in Example 1.

[0095] The aged-resistant IRMOF-1-NH 2 / SBS modified asphalt is composed of the following raw materials by mass fraction: asphalt 98.00%, IRMOF-1-NH 2 / SBS composite modifier 1.50%, sulfur 0.50%;

[0096] The aged-resistant IRMOF-1-NH 2 / SBS modified asphalt is prepared in the same way as in Example 1.

[0097] That is, compared with Example 1, a small amount of IRMOF-1-NH 2 / SBS composite modifier is used to modify asphalt in this comparative example.

[0098] Comparative Example 5

[0099] The IRMOF-1-NH 2 / SBS composite modifier and its preparation method are the same as those in Example 1.

[0100] The aged-resistant IRMOF-1-NH 2 / SBS modified asphalt is composed of the following raw materials by mass fraction: asphalt 79.00%, IRMOF-1-NH 2 / SBS composite modifier 20.50%, sulfur 0.50%;

[0101] The aged-resistant IRMOF-1-NH 2 / SBS modified asphalt is prepared in the same way as in Example 1.

[0102] That is, compared with Example 1, a large amount of IRMOF-1-NH 2 / SBS composite modifier is used to modify asphalt in this comparative example.

[0103] Test on anti-aging performance of modified asphalt

[0104] The modified asphalts prepared in the above examples and comparative examples were respectively subjected to short-term thermal-oxidative aging (RTFOT, temperature of 163 °C, aging time of 5 hours) and ultraviolet accelerated aging test (UV, ultraviolet light intensity of 1200 μW / cm 2 , temperature of 60 °C, aging time of 9 days); then the properties of each specimen before and after aging were respectively tested, and the residual penetration (residual penetration = penetration after aging / penetration before aging × 100%), softening point increment (softening point increment = softening point after aging - softening point before aging), and ductility retention rate (ductility retention rate = ductility after aging / ductility before aging × 100%) were calculated. The test results are listed in Table 1.

[0105] Table 1 Test results of anti-aging performance of modified asphalt

[0106]

[0107] As can be seen from Table 1, the modified asphalt prepared with the composite modifier of the present invention has excellent anti-aging performance. Compared with Example 1, the composite modifier of Comparative Example 1 lacks IRMOF-1-NH 2 , and the composite modifier of Comparative Example 2 lacks SBS. After the obtained modified asphalt undergoes thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rate are both smaller than those of the modified asphalt prepared with the IRMOF-1-NH 2 / SBS composite modifier of the present invention, while the softening point increment is greater than that of the modified asphalt prepared in the present invention; it shows that IRMOF-1-NH 2 can cooperate with SBS to improve the modification effect of the composite modifier. Under the combined action of IRMOF-1-NH 2 and SBS, the composite modifier can significantly improve the anti-aging performance of asphalt, and the obtained modified asphalt has better heat-resistant oxidative aging and ultraviolet aging performance. Compared with Example 1, in Comparative Example 3, SBS was omitted, and at the same time, IRMOF-1 was not amino-functionalized. The composite modifier was directly composed of IRMOF-1, accelerator, and compatibilizer. After the obtained modified asphalt undergoes thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rate are also both smaller than those of the modified asphalt prepared with the composite modifier of the present invention, while the softening point increment is greater than that of the modified asphalt prepared in the present invention. By comparing Comparative Example 2 and Comparative Example 3, it can be known that amino-functionalizing IRMOF-1 can effectively improve the anti-aging performance of asphalt. Compared with Example 1, in Comparative Example 4, a small amount of IRMOF-1-NH 2 / SBS composite modifier was used to modify asphalt. After the obtained modified asphalt undergoes thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rate are both smaller than those of the modified asphalt prepared in the present invention, while the softening point increment is greater than that of the modified asphalt prepared in the present invention; compared with Example 1, in Comparative Example 5, a large amount of IRMOF-1-NH2 The asphalt modified by the IRMOF-1-NH / SBS composite modifier, after the obtained modified asphalt undergoes thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rates are both less than those of the modified asphalt prepared in the present invention, while the softening point increment is greater than that of the modified asphalt prepared in the present invention; this indicates that using too little or too much IRMOF-1-NH 2 / SBS composite modifier to prepare modified asphalt does not yield good results, and the IRMOF-1-NH 2 / SBS composite modifier should be used appropriately.

[0108] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An IRMOF-1-NH2 / SBS composite modifier, characterized in that: In terms of mass fraction, the following raw materials are included: IRMOF-1-NH2 28%~35%, SBS 53%~61%, accelerator 0.2%~0.4%, compatibilizer 10.6%~14.6%; The preparation method of IRMOF-1-NH2 comprises the following steps: S1. Add soluble zinc salt and 2-aminoterephthalic acid into a solvent, perform ultrasonic treatment, react at 100-150° C. for 12-24 hours, and obtain a solid product after separation and washing; S2. The solid product obtained in step S1 is heated at 100-150° C. for 10-20 h to obtain IRMOF-1-NH2 crystals.

2. An IRMOF-1-NH2 / SBS composite modifier according to claim 1, characterized in that: Calculated by mass fraction, the following raw materials are included: IRMOF-1-NH2 32%, SBS 53%, accelerator 0.4%, and compatibilizer 14.6%.

3. An IRMOF-1-NH2 / SBS composite modifier according to claim 1, characterized in that: The mass ratio of the soluble zinc salt to 2-aminoterephthalic acid is (3-4.5):

1.

4. An IRMOF-1-NH2 / SBS composite modifier according to claim 3, characterized in that: The mass ratio of the soluble zinc salt to 2-aminoterephthalic acid is 3.5:

1.

5. The IRMOF-1-NH2 / SBS composite modifier according to claim 1, characterized in that: In step S1, the soluble zinc salt is at least one of zinc chloride, zinc nitrate, and zinc acetate; and / or the concentration of the soluble zinc salt in the solvent is 2%wt~5%wt.

6. The IRMOF-1-NH2 / SBS composite modifier according to claim 1, characterized in that: In step S1, the solvent is at least one of N,N-dimethylformamide, γ-valerolactone, N,N-diethylformamide, and ethanol.

7. The IRMOF-1-NH2 / SBS composite modifier according to claim 1, characterized in that: The accelerator is at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide and bis(1,5-pentylene)thiuram tetrasulfide; and the compatibilizer is catalytic oil slurry.

8. The method for preparing the IRMOF-1-NH2 / SBS composite modifier according to any one of claims 1 to 7, characterized in that: The following steps are involved: P1. Prepare the IRMOF-1-NH2, SBS, accelerator and compatibilizer according to their respective mass fractions, and then blend them in a mixer at a blending temperature of 90-100°C and a blending speed of 1300-1500 r / min to obtain a blend; P2. Add the blend obtained in step P1 into a granulator for granulation to obtain the IRMOF-1-NH2 / SBS composite modifier.

9. An aging-resistant IRMOF-1-NH2 / SBS modified asphalt, characterized in that: The invention comprises the following raw materials in mass fractions: 89.5% to 93.5% of asphalt, 6% to 10% of the IRMOF-1-NH2 / SBS composite modifier described in any one of claims 1 to 7, and 0.1% to 1.0% of a stabilizer.

10. The method for preparing the aging-resistant IRMOF-1-NH2 / SBS modified asphalt according to claim 9, characterized in that: The following steps are involved: Prepare the asphalt, IRMOF-1-NH2 / SBS composite modifier and stabilizer according to their respective mass fractions; then heat the asphalt to a fluid state, slowly add the IRMOF-1-NH2 / SBS composite modifier and stabilizer while stirring, maintain the temperature at 160-180°C, stir at a speed of 4000-6000 rpm for 1-3 hours, and then continue stirring at a speed of 400-600 rpm for 1-3 hours to obtain the aging-resistant IRMOF-1-NH2 / SBS modified asphalt.

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