Anti-aging IRMOF-1-Cu (II) / SBS composite modifier and preparation method and application thereof

Abstract

The invention provides an anti-aging IRMOF-1-Cu (II) / SBS composite modifier as well as a preparation method and application thereof, and belongs to the technical field of asphalt processing. The preparation method comprises the following steps: carrying out structure regulation and control on IRMOF-1, introducing a defect site, and modifying a structure defect by using monatomic metal Cu (II), so as to prepare IRMOF-1-Cu (II); and then preparing the IRMOF-1-Cu (II) / SBS composite modifier according to the following raw materials in percentage by weight: 27%-37% of IRMOF-1-Cu (II), 52%-60% of SBS, 0.2%-0.4% of an accelerant and 10.8%-14.6% of a compatilizer. According to the present invention, the IRMOF-1-Cu (II) and the SBS in the prepared composite modifier have good compatibility stability, the composite modifier is applied to the anti-aging asphalt, the composite modifier can efficiently store aromatic components so as to achieve the gelation inhibition effect, and the IRMOF-1-Cu (II) and the SBS can synergistically improve the modification effect of the composite modifier so as to achieve the anti-aging effect of the anti-aging asphalt. The anti-aging performance of the asphalt is further obviously improved.

Description

Technical Field

[0001] The present invention relates to the technical field of asphalt processing, and particularly relates to an anti-aging IRMOF-1-Cu(II) / SBS composite modifier, a preparation method thereof, and an application thereof. Background Art

[0002] Ordinary asphalt has poor performance under high and low temperature conditions, which easily leads to pavement diseases such as ruts and potholes, and has a short service life. Especially in a heavy traffic environment, the pavement damage is more serious. To improve this situation, polymers are usually used to modify asphalt to enhance its road performance. Among them, styrene-butadiene-styrene triblock copolymer (SBS) is a commonly used modifier. It forms a network structure in asphalt through physical cross-linking, significantly enhancing the high-temperature rutting resistance and low-temperature crack resistance of asphalt. Therefore, SBS modified asphalt pavements have been widely used worldwide. However, during long-term use, SBS modified asphalt pavements are subjected to the combined action of natural factors such as heat, moisture, ultraviolet rays, and oxygen, as well as vehicle loads, resulting in complex physical and chemical changes. These changes will cause the aging degradation of SBS modified asphalt, thereby deteriorating the asphalt performance, and ultimately triggering pavement diseases such as ruts, spalling, cracks, and potholes, seriously affecting the durability of asphalt pavements. Whether it is thermal-oxidative aging or ultraviolet aging, the aging process of asphalt usually shows a transformation of components and structures: aromatic fraction → resin → asphaltene. Specifically, the aromatic fraction and resin will gradually react and decrease, resulting in the gradual gelation of the colloidal structure of asphalt. This process will significantly reduce the performance of asphalt, such as an increase in viscosity, a decrease in ductility and adhesion, etc., thus greatly shortening the service life of asphalt pavements. It can be seen that retaining the aromatic components in asphalt and inhibiting the gelation of its structure are the keys to improving the anti-aging performance of asphalt.

[0003] Metal-organic framework materials (MOFs), as a new type of porous material, have high specific surface area, adjustable pore size, and surface chemical properties, and have shown great application potential in the fields of gas storage, separation, catalysis, etc. in recent years. The structural diversity and designability of MOF materials also make them have certain application prospects in the field of asphalt modification. At present, the prior art proposes to generate functional derivatives by introducing different functional groups into MOFs (for example, MOFs-R, R = NH2, OH, COOH, etc.). However, due to the limited active sites provided by the functional groups, their application effects in asphalt modification are not ideal; and the introduction of functional groups may block pores, reduce the specific surface area, affect the adsorption efficiency, resulting in an unsatisfactory anti-aging effect.

[0004] In order to overcome the limitations of MOFs-R in asphalt modification, the present invention proposes a novel IRMOF-1-Cu(II) / SBS modifier. By regulating the structure of IRMOF-1, introducing defect sites, and modifying the structural defects with single-atom metals, the adsorption capacity of aromatic components in asphalt is enhanced. This method is of great significance for improving the performance of SBS modified asphalt. Summary of the Invention

[0005] Aiming at the deficiencies of the above prior art, the present invention provides an anti-aging IRMOF-1-Cu(II) / SBS composite modifier, its preparation method and application. On the one hand, the present invention enables the long-term and efficient storage of aromatic components in asphalt by regulating the structure of IRMOF-1-Cu(II), inhibiting the gelation of the asphalt structure; on the other hand, the present invention introduces Cu(II) as an active site to chemically interact with benzene series molecules in asphalt to form stable chemical adsorption. This chemical adsorption not only increases the adsorption amount of benzene series substances but also enhances the selectivity for benzene series substances; moreover, the introduced IRMOF-1-Cu(II) structure contains benzene rings, so it also has the ability to absorb ultraviolet light.

[0006] To achieve the above object, the specific technical solutions of the present invention are as follows:

[0007] In the first aspect, the present invention provides an IRMOF-1-Cu(II) / SBS composite modifier, which includes the following raw materials in terms of mass fraction: 27% - 37% of IRMOF-1-Cu(II), 52% - 60% of SBS, 0.2% - 0.4% of accelerator, and 10.8% - 14.6% of compatibilizer;

[0008] Among them, the preparation method of the IRMOF-1-Cu(II) includes the following steps:

[0009] S1. Mix soluble zinc salt, terephthalic acid and a solvent evenly, add an appropriate amount of monocarboxylic acid, and react at 100 - 150 °C; centrifuge to collect the precipitate product, wash and dry it to obtain defective metal-organic framework IRMOF-1 crystals, denoted as IRMOF-1-defect;

[0010] S2. Mix IRMOF-1-defect, soluble copper salt and a solvent evenly, and react at 80 - 100 °C; centrifuge to collect the precipitate product and wash it to obtain IRMOF-1-Cu(II).

[0011] In the composite modifier of the present invention, IRMOF-1-Cu(II) can efficiently store aromatic components during the aging process of asphalt, thereby inhibiting the gelation of the asphalt structure and enhancing the anti-aging performance of asphalt; in addition, IRMOF-1-Cu(II) has good compatibility with SBS, and IRMOF-1-Cu(II) and SBS can synergistically improve the modification effect of the composite modifier, significantly enhancing the anti-aging performance of asphalt. Further, in the present invention, a monocarboxylic acid is used as a regulator to regulate the structure of IRMOF-1, introduce defect sites, and modify the structural defects with single-atom metal Cu(II); on the one hand, Cu(II) serves as an active site and undergoes Cu II ···π benzene interactions with benzene series molecules in asphalt to form stable chemisorption. This chemisorption not only increases the adsorption amount of benzene series substances but also enhances the selectivity for benzene series substances; on the other hand, O-H framework ···π benzene 、π framework ···π benzene and Cu II ···π benzene The three interactions cooperate synergistically to further enhance the adsorption effect.

[0012] Further, in step S1, the molar ratio of the soluble zinc salt to terephthalic acid is 2:1.

[0013] Further, in step S1, the mass ratio of terephthalic acid to monocarboxylic acid is 1:(4~18).

[0014] Furthermore, in step S1, the mass ratio of terephthalic acid to monocarboxylic acid is 1:11.

[0015] Further, in step S1, the soluble zinc salt includes but is not limited to at least one of zinc chloride, zinc nitrate, and zinc acetate.

[0016] Further, in step S1, the concentration of the soluble zinc salt in the solvent is 2%wt~5%wt.

[0017] Further, in step S1, the monocarboxylic acid includes but is not limited to at least one of formic acid, acetic acid, and benzoic acid.

[0018] Further, in steps S1 and S2, the solvent includes but is not limited to at least one of N,N-dimethylformamide, γ-valerolactone, N,N-diethylformamide, and ethanol.

[0019] Further, in step S1, the reaction time is 12~24 h.

[0020] Further, in steps S1 and S2, the washing liquid used in the washing process is N,N-dimethylformamide and methanol.

[0021] Further, in step S1, the drying temperature is 80 - 120 °C and the time is 10 - 20 h.

[0022] Further, in step S2, the mass ratio of IRMOF-1-defect to the soluble copper salt is 1:1.

[0023] Further, in step S2, the soluble copper salt includes but is not limited to at least one of copper chloride and copper nitrate.

[0024] Further, in step S2, the reaction time is 20 - 30 h.

[0025] Further, the accelerator includes but is not limited to at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and bis(1,5-pentamethylene)tetramthiuram disulfide.

[0026] Further, the compatibilizer includes but is not limited to catalytic slurry.

[0027] In a second aspect, the present invention provides a method for preparing the IRMOF-1-Cu(II) / SBS composite modifier, comprising the following steps:

[0028] Mix IRMOF-1-Cu(II), SBS, accelerator, and compatibilizer evenly and then granulate to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

[0029] Further, the mixing process is carried out in a mixer, the mixing temperature is 90 - 100 °C, and the mixing speed is 1300 - 1500 r / min.

[0030] In a third aspect, the present invention provides the application of the IRMOF-1-Cu(II) / SBS composite modifier in the preparation of aging-resistant asphalt.

[0031] In a fourth aspect, the present invention provides an aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt, which, by mass fraction, comprises the following raw materials: 89.5% - 93.5% asphalt, 6% - 10% IRMOF-1-Cu(II) / SBS composite modifier, and 0.5% stabilizer.

[0032] Further, the asphalt is petroleum asphalt, with a penetration at 25 °C of 60 - 120 dmm, a softening point of 40 - 55 °C, and an elongation at 10 °C of 15 - 25 cm.

[0033] Further, the stabilizer includes but is not limited to sulfur.

[0034] In a fifth aspect, the present invention provides a method for preparing the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt, comprising the following steps:

[0035] Heat the asphalt to a flowing state, and slowly add the RMOF-1-Cu(II) / SBS composite modifier and the stabilizer while stirring, keep the temperature at 160-180 °C, and stir at a rotation speed of 4000-6000 rpm for 1-3 h; continue to maintain 160-180 °C, and then continue to stir at a rotation speed of 400-600 rpm for 1-3 h to obtain the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] (1) In the IRMOF-1-Cu(II) / SBS of the present invention, by adjusting metal ions and organic ligands, the pore characteristics and surface chemical characteristics are designed and regulated. When benzene series substances volatilize during the aging process of asphalt, IRMOF-1-Cu(II) can efficiently store them, achieving the purpose of storing aromatic components to inhibit the gelation of the asphalt structure, that is, it can effectively improve the anti-aging performance of asphalt.

[0038] (2) In the present invention, IRMOF-1-Cu(II) / SBS not only has O-H framework ···π benzene and π framework ···π benzene interactions, but also introduces Cu(II) as an active site to have Cu II ···π benzene interactions with benzene series molecules in asphalt to form stable chemical adsorption. This chemical adsorption not only increases the adsorption amount of benzene series substances, but also enhances the selectivity for benzene series substances. In addition, the three interactions of O-H framework ···π benzene 、π framework ···π benzene and Cu II ···π benzene synergistically can further enhance the adsorption effect.

[0039] (3) The IRMOF-1-Cu(II) / SBS of the present invention has benzene rings, and together with the benzene rings in the stored aromatic components, it has excellent ultraviolet absorption ability, which can inhibit the influence of ultraviolet light on asphalt, that is, it can effectively improve the anti-aging performance of asphalt.

[0040] (4) The presence of the organic ligand in the IRMOF-1-Cu(II) structure of the composite modifier of the present invention can enhance the affinity between the MOF material and the SBS particles, so that the two have good compatibility and stability. IRMOF-1-Cu(II) and SBS can synergistically improve the modification effect of the composite modifier and significantly enhance the anti-aging performance of asphalt. Specific Embodiments

[0041] 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. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0042] In the first aspect, the present invention provides an IRMOF-1-Cu(II) / SBS composite modifier, which includes the following raw materials in terms of mass fraction: 27% - 37% of IRMOF-1-Cu(II), 52% - 60% of SBS, 0.2% - 0.4% of accelerator, and 10.8% - 14.6% of compatibilizer;

[0043] Among them, the preparation method of the IRMOF-1-Cu(II) includes the following steps:

[0044] S1. Mix soluble zinc salt and terephthalic acid in a molar ratio of 2:1 with a solvent, add an appropriate amount of monocarboxylic acid, and react at 100 - 150 °C for 12 - 24 h; Centrifuge to collect the precipitate product, wash it, and dry it at 80 - 120 °C for 10 - 20 h to obtain defective metal-organic framework IRMOF-1 crystals, denoted as IRMOF-1-defect;

[0045] S2. Mix IRMOF-1-defect and soluble copper salt in a mass ratio of 1:1 with a solvent, and react at 80 - 100 °C for 20 - 30 h; Centrifuge to collect the precipitate product and wash it to obtain IRMOF-1-Cu(II).

[0046] In some examples, the mass ratio of the terephthalic acid to the monocarboxylic acid is 1:(4 - 18).

[0047] In some examples, the soluble zinc salt includes but is not limited to at least one of zinc chloride, zinc nitrate, and zinc acetate.

[0048] In some examples, the concentration of the soluble zinc salt in the solvent is 2%wt - 5%wt.

[0049] In some examples, the monocarboxylic acid includes but is not limited to at least one of formic acid, acetic acid, and benzoic acid.

[0050] In some examples, in steps S1 and S2, the solvent includes but is not limited to at least one of N,N-dimethylformamide, γ-valerolactone, N,N-diethylformamide, and ethanol.

[0051] In some examples, the soluble copper salt includes but is not limited to at least one of copper chloride and copper nitrate.

[0052] In some examples, the accelerator includes but is not limited to at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and bis(1,5-pentamethylene)tetramthiuram disulfide.

[0053] The preparation method of the IRMOF-1-Cu(II) / SBS composite modifier includes the following steps:

[0054] Mix IRMOF-1-Cu(II), SBS, accelerator, and compatibilizer evenly in a mixer at a mixing temperature of 90 - 100 °C and a mixing speed of 1300 - 1500 r / min; granulate to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

[0055] In the following specific examples and comparative examples, all raw materials are common raw materials on the market. Among them, the soluble zinc salt, soluble copper salt, and N,N-dimethylformamide are purchased from Shanghai Macklin Biochemical Co., Ltd.; the terephthalic acid is purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd.; the methanol is purchased from Shanghai Titan Technology Co., Ltd.; the SBS is purchased from Yueyang Baling Petrochemical Co., Ltd., Hunan; the tetramethylthiuram disulfide is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; the catalytic oil slurry is purchased from the Changqing Oilfield Branch of PetroChina Co., Ltd.; the asphalt is road petroleum asphalt with a penetration at 25 °C of 60 - 120 dmm, a softening point of 40 - 55 °C, and an elongation at 10 °C of 15 - 25 cm.

[0056] Example 1

[0057] An IRMOF-1-Cu(II) / SBS composite modifier, by mass fraction, consists of the following raw materials: 33.00% IRMOF-1-Cu(II), 54.00% SBS, 0.40% tetramethylthiuram disulfide, and 12.60% catalytic oil slurry;

[0058] Among them, the preparation method of IRMOF-1-Cu(II) is as follows:

[0059] S1. Mix 2 mmol of zinc nitrate hexahydrate, 1 mmol of terephthalic acid with N,N-dimethylformamide (the mass ratio of terephthalic acid to N,N-dimethylformamide is 1:100), add 1.5 mL of formic acid as a regulator, dissolve it by ultrasonic, then load it into a polytetrafluoroethylene reaction kettle, react at 120 °C for 12 h, and centrifuge to collect the precipitate product; wash the product 3 times with N,N-dimethylformamide and methanol respectively and centrifuge to collect; place the product in an oven at 120 °C and dry it for 12 h to obtain metal-organic framework IRMOF-1-defect crystals.

[0060] S2. Add IRMOF-1-defect (500 mg) to a mixture of copper(II) chloride (500 mg) and N,N-dimethylformamide (10 mL), and then react at 85 °C for 24 h; after naturally cooling to room temperature, centrifuge to collect the precipitate product, and wash it several times with N,N-dimethylformamide and methanol to obtain IRMOF-1-Cu(II) crystals.

[0061] The preparation method of the IRMOF-1-Cu(II) / SBS composite modifier in this example is as follows:

[0062] P1. Place IRMOF-1-Cu(II), 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;

[0063] P2. Add the mixture obtained in step P1 to a single-screw granulator for extrusion granulation, and the head temperature is 165 °C to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

[0064] Use the IRMOF-1-Cu(II) / SBS composite modifier prepared in Example 1 to prepare aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt. The aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is composed of the following raw materials by mass fraction: asphalt 91.50%, IRMOF-1-Cu(II) / SBS composite modifier 8.00%, sulfur 0.50%;

[0065] The preparation method of the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is as follows:

[0066] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and slowly add the IRMOF-1-Cu(II) / SBS composite modifier and sulfur while maintaining 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 maintain 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt.

[0067] Example 2

[0068] An IRMOF-1-Cu(II) / SBS composite modifier, by mass fraction, consists of the following raw materials: 37.00% IRMOF-1-Cu(II), 52.00% SBS, 0.20% tetramethylthiuram disulfide, and 10.80% catalytic slurry.

[0069] Among them, the preparation method of IRMOF-1-Cu(II) is as follows:

[0070] S1. Mix 2 mmol of zinc nitrate hexahydrate, 1 mmol of terephthalic acid with N,N-dimethylformamide (the mass ratio of terephthalic acid to N,N-dimethylformamide is 1:100), add 1.5 mL of formic acid as a regulator, ultrasonically dissolve it, then load it into a polytetrafluoroethylene reaction kettle, react at 120 °C for 12 h, and centrifuge to collect the precipitate product. Wash the product 3 times with N,N-dimethylformamide and methanol respectively and centrifuge to collect; place the product in an oven at 120 °C and dry it for 12 h to obtain the metal-organic framework IRMOF-1-defect crystal.

[0071] S2. Add IRMOF-1-defect (500 mg) to a mixture of copper(II) chloride (500 mg) and N,N-dimethylformamide (10 mL), and then react at 85 °C for 24 h; after naturally cooling to room temperature, centrifuge to collect the precipitate product, and wash it several times with N,N-dimethylformamide and methanol to obtain IRMOF-1-Cu(II) crystals.

[0072] The preparation method of the IRMOF-1-Cu(II) / SBS composite modifier in this example is as follows:

[0073] P1. Place IRMOF-1-Cu(II), 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.

[0074] P2. Add the mixture obtained in step P1 into a single-screw granulator for extrusion granulation. The head temperature is 165 °C to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

[0075] Use the IRMOF-1-Cu(II) / SBS composite modifier prepared in Example 2 to prepare the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt. The anti-aging IRMOF-1-Cu(II) / SBS modified asphalt is composed of the following raw materials by mass fraction: asphalt 93.50%, IRMOF-1-Cu(II) / SBS composite modifier 6.00%, sulfur 0.50%.

[0076] The preparation method of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt is as follows:

[0077] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and simultaneously slowly add the IRMOF-1-Cu(II) / 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 maintain 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt.

[0078] Example 3

[0079] An IRMOF-1-Cu(II) / SBS composite modifier is composed of the following raw materials by mass fraction: 27.00% IRMOF-1-Cu(II), 60.00% SBS, 0.40% tetramethylthiuram disulfide, 12.60% catalytic slurry.

[0080] Among them, the preparation method of IRMOF-1-Cu(II) is as follows:

[0081] S1. Mix 2 mmol of zinc nitrate hexahydrate, 1 mmol of terephthalic acid with N,N-dimethylformamide (the mass ratio of terephthalic acid to N,N-dimethylformamide is 1:100), add 1.5 mL of formic acid as a regulator, ultrasonically dissolve and then load it into a polytetrafluoroethylene reaction kettle, react at 120 °C for 12 h, and centrifuge to collect the precipitate product; wash the product 3 times with N,N-dimethylformamide and methanol respectively and centrifuge to collect; place the product in an oven at 120 °C and dry it for 12 h to obtain the metal-organic framework IRMOF-1-defect crystal.

[0082] S2. Add IRMOF-1-defect (500 mg) to a mixture of copper(II) chloride (500 mg) and N,N-dimethylformamide (10 mL), and then react at 85 °C for 24 h; after naturally cooling to room temperature, centrifuge to collect the precipitated product, and wash it several times with N,N-dimethylformamide and methanol to obtain IRMOF-1-Cu(II) crystals.

[0083] The preparation method of the IRMOF-1-Cu(II) / SBS composite modifier in this example is as follows:

[0084] P1. Place IRMOF-1-Cu(II), 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.

[0085] P2. Add the mixture obtained in step P1 to a single-screw granulator for extrusion granulation. The head temperature is 165 °C to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

[0086] The IRMOF-1-Cu(II) / SBS composite modifier prepared in Example 3 is used to prepare aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt. The aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is composed of the following raw materials by mass fraction: asphalt 89.50%, IRMOF-1-Cu(II) / SBS composite modifier 10.00%, sulfur 0.50%.

[0087] The preparation method of the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is as follows:

[0088] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and simultaneously slowly add the IRMOF-1-Cu(II) / 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 maintain 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt.

[0089] Example 4

[0090] An IRMOF-1-Cu(II) / SBS composite modifier is composed of the following raw materials by mass fraction: 33.00% IRMOF-1-Cu(II), 54.00% SBS, 0.40% tetramethylthiuram disulfide, 12.60% catalytic slurry.

[0091] Among them, the preparation method of IRMOF-1-Cu(II) is as follows:

[0092] S1. Mix 2 mmol of zinc nitrate hexahydrate, 1 mmol of terephthalic acid with N,N-dimethylformamide (the mass ratio of terephthalic acid to N,N-dimethylformamide is 1:100), add 0.5 mL of formic acid as a regulator, ultrasonically dissolve it, then load it into a polytetrafluoroethylene reaction kettle, react at 120 °C for 12 h, and centrifuge to collect the precipitate product; wash the product 3 times with N,N-dimethylformamide and methanol respectively and centrifuge to collect; place the product in an oven at 120 °C and dry it for 12 h to obtain metal-organic framework IRMOF-1-defect crystals.

[0093] S2. Add IRMOF-1-defect (500 mg) to a mixture of copper(II) chloride (500 mg) and N,N-dimethylformamide (10 mL), and then react at 85 °C for 24 h; after naturally cooling to room temperature, centrifuge to collect the precipitate product, and wash it several times with N,N-dimethylformamide and methanol to obtain IRMOF-1-Cu(II) crystals.

[0094] The preparation method of the IRMOF-1-Cu(II) / SBS composite modifier in this example is as follows:

[0095] P1. Blend IRMOF-1-Cu(II), SBS, tetramethylthiuram disulfide and catalytic slurry in a high-speed mixer (model: SHR-5A), the blending temperature is 95 °C, the speed is 1300 r / min, and the time is 8 min to obtain a mixture;

[0096] P2. Add the mixture obtained in step P1 to a single-screw granulator and extrude and granulate, the head temperature is 165 °C to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

[0097] The IRMOF-1-Cu(II) / SBS composite modifier prepared in Example 1 is used to prepare aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt. The aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is composed of the following raw materials by mass fraction: asphalt 91.50%, IRMOF-1-Cu(II) / SBS composite modifier 8.00%, sulfur 0.50%;

[0098] The preparation method of the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is as follows:

[0099] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and slowly add the IRMOF-1-Cu(II) / SBS composite modifier and sulfur while maintaining the temperature at 165 °C. Start the high-speed shearing machine and stir at a speed of 5000 rpm for 1.5 h; continue to maintain 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt.

[0100] Example 5

[0101] An IRMOF-1-Cu(II) / SBS composite modifier, by mass fraction, consists of the following raw materials: 33.00% IRMOF-1-Cu(II), 54.00% SBS, 0.40% tetramethylthiuram disulfide, and 12.60% catalytic slurry;

[0102] Among them, the preparation method of IRMOF-1-Cu(II) is as follows:

[0103] S1. Mix 2 mmol of zinc nitrate hexahydrate, 1 mmol of terephthalic acid with N,N-dimethylformamide (the mass ratio of terephthalic acid to N,N-dimethylformamide is 1:100), add 2.5 mL of formic acid as a regulator, ultrasonically dissolve and then load it into a polytetrafluoroethylene reaction kettle, react at 120 °C for 12 h, and centrifuge to collect the precipitate product; wash the product 3 times with N,N-dimethylformamide and methanol respectively and centrifuge to collect; place the product in an oven at 120 °C and dry for 12 h to obtain the metal-organic framework IRMOF-1-defect crystal.

[0104] S2. Add IRMOF-1-defect (500 mg) to a mixture of copper(II) chloride (500 mg) and N,N-dimethylformamide (10 mL), and then react at 85 °C for 24 h; after naturally cooling to room temperature, centrifuge to collect the precipitate product, and wash it several times with N,N-dimethylformamide and methanol to obtain IRMOF-1-Cu(II) crystals.

[0105] The preparation method of the IRMOF-1-Cu(II) / SBS composite modifier in this example is as follows:

[0106] P1. Place IRMOF-1-Cu(II), 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;

[0107] P2. Add the mixture obtained in step P1 into a single-screw granulator for extrusion granulation. The head temperature is 165 °C to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

[0108] Use the IRMOF-1-Cu(II) / SBS composite modifier prepared in Example 1 to prepare the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt. The aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is composed of the following raw materials by mass fraction: 91.50% asphalt, 8.00% IRMOF-1-Cu(II) / SBS composite modifier, and 0.50% sulfur.

[0109] The preparation method of the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is as follows:

[0110] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and simultaneously slowly add the IRMOF-1-Cu(II) / 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 maintain 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt.

[0111] Comparative Example 1

[0112] An SBS composite modifier is composed of the following raw materials by mass fraction: 87.00% SBS, 0.40% tetramethylthiuram disulfide, and 12.60% catalytic slurry.

[0113] The preparation method of the SBS composite modifier in this comparative example is as follows:

[0114] P1. Place 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.

[0115] P2. Add the mixture obtained in step P1 into a single-screw granulator for extrusion granulation. The head temperature is 165 °C to obtain the SBS composite modifier.

[0116] Use the SBS composite modifier prepared in Comparative Example 1 to prepare the aging-resistant SBS modified asphalt. The aging-resistant SBS modified asphalt is composed of the following raw materials by mass fraction: 91.50% asphalt, 8.00% SBS composite modifier, and 0.50% sulfur.

[0117] The preparation method of the aging-resistant SBS modified asphalt is as follows:

[0118] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and slowly add the SBS composite modifier and sulfur while maintaining the temperature at 165 °C. Start the high-speed shearing machine and stir at a speed of 5000 rpm for 1.5 h; continue to maintain 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.

[0119] Comparative Example 2

[0120] An IRMOF-1-Cu(II) composite modifier, by mass fraction, consists of the following raw materials: 87.00% IRMOF-1-Cu(II), 0.40% tetramethylthiuram disulfide, and 12.60% catalytic slurry;

[0121] Among them, the preparation method of IRMOF-1-Cu(II) is the same as that in Example 1.

[0122] The preparation method of the IRMOF-1-Cu(II) composite modifier in this comparative example is as follows:

[0123] P1. Place IRMOF-1-Cu(II), 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;

[0124] P2. Add the mixture obtained in step P1 to a single-screw granulator for extrusion granulation. The head temperature is 165 °C to obtain the IRMOF-1-Cu(II) composite modifier.

[0125] Use the IRMOF-1-Cu(II) composite modifier prepared in Comparative Example 2 to prepare the aging-resistant IRMOF-1-Cu(II) modified asphalt. The aging-resistant IRMOF-1-Cu(II) modified asphalt, by mass fraction, consists of the following raw materials: 91.50% asphalt, 8.00% IRMOF-1-Cu(II) / SBS composite modifier, and 0.50% sulfur;

[0126] The preparation method of the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt is as follows:

[0127] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and slowly add the IRMOF-1-Cu(II) composite modifier and sulfur while maintaining the temperature at 165 °C. Start the high-speed shearer and stir at a speed of 5000 rpm for 1.5 h; continue to maintain 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the aging-resistant IRMOF-1-Cu(II) modified asphalt.

[0128] Comparative Example 3

[0129] An IRMOF-1-defect / SBS composite modifier, by mass fraction, consists of the following raw materials: 33.00% IRMOF-1-defect, 54.00% SBS, 0.40% tetramethylthiuram disulfide, and 12.60% catalytic slurry;

[0130] Among them, the preparation method of IRMOF-1-defect is as follows:

[0131] S1. Mix 2 mmol of zinc nitrate hexahydrate, 1 mmol of terephthalic acid with N,N-dimethylformamide (the mass ratio of terephthalic acid to N,N-dimethylformamide is 1:100), add 1.5 mL of formic acid as a regulator, ultrasonically dissolve and then load it into a polytetrafluoroethylene reaction kettle, react at 120 °C for 12 h, and centrifuge to collect the precipitate product; wash the product 3 times with N,N-dimethylformamide and methanol respectively and centrifuge to collect; place the product in an oven at 120 °C and dry for 12 h to obtain IRMOF-1-defect.

[0132] The preparation method of the IRMOF-1-defect / SBS composite modifier in this comparative example is as follows:

[0133] P1. Place IRMOF-1-defect, 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;

[0134] P2. Add the mixture obtained in step P1 to a single-screw granulator and extrude and granulate. The head temperature is 165 °C to obtain the IRMOF-1-defect / SBS composite modifier.

[0135] The IRMOF-1-defect / SBS composite modifier prepared in Comparative Example 3 was used to prepare the anti-aging IRMOF-1-defect / SBS modified asphalt. The anti-aging IRMOF-1-defect / SBS modified asphalt was composed of the following raw materials by mass fraction: asphalt 91.50%, IRMOF-1-defect / SBS composite modifier 8.00%, sulfur 0.50%.

[0136] The preparation method of the anti-aging IRMOF-1-defect / SBS modified asphalt was as follows:

[0137] The asphalt was heated to a flowing state and stirred at a rotation speed of 500 rpm. At the same time, the IRMOF-1-defect / SBS composite modifier and sulfur were slowly added, and the temperature was maintained at 165 °C. Then, a high-speed shearing machine was started and stirred at a rotation speed of 5000 rpm for 1.5 h. The temperature of 165 °C was continuously maintained, and then it was continuously stirred at a rotation speed of 500 rpm for 2.5 h to obtain the anti-aging IRMOF-1-defect / SBS modified asphalt.

[0138] Comparative Example 4

[0139] The IRMOF-1-Cu(II) / SBS composite modifier prepared in Example 1 was used to prepare the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt. The anti-aging IRMOF-1-Cu(II) / SBS modified asphalt was composed of the following raw materials by mass fraction: asphalt 98.50%, IRMOF-1-Cu(II) / SBS composite modifier 1.00%, sulfur 0.50%.

[0140] The preparation method of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt was as follows:

[0141] The asphalt was heated to a flowing state and stirred at a rotation speed of 500 rpm. At the same time, the IRMOF-1-Cu(II) / SBS composite modifier and sulfur were slowly added, and the temperature was maintained at 165 °C. Then, a high-speed shearing machine was started and stirred at a rotation speed of 5000 rpm for 1.5 h. The temperature of 165 °C was continuously maintained, and then it was continuously stirred at a rotation speed of 500 rpm for 2.5 h to obtain the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt.

[0142] Comparative Example 5

[0143] The IRMOF-1-Cu(II) / SBS composite modifier prepared in Example 1 was used to prepare the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt. The anti-aging IRMOF-1-Cu(II) / SBS modified asphalt was composed of the following raw materials by mass fraction: asphalt 79.50%, IRMOF-1-Cu(II) / SBS composite modifier 20.00%, sulfur 0.50%.

[0144] The preparation method of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt is as follows:

[0145] Heat the asphalt to a flowing state, stir at a speed of 500 rpm, and slowly add the IRMOF-1-Cu(II) / SBS composite modifier and sulfur while maintaining the temperature at 165 °C. Start the high-speed shearer and stir at a speed of 5000 rpm for 1.5 h; continue to maintain 165 °C, and then continue to stir at a speed of 500 rpm for 2.5 h to obtain the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt.

[0146] Test on the anti-aging performance of modified asphalt

[0147] The modified asphalts prepared in Examples 1-5 and Comparative Examples 1-5 were respectively subjected to short-term thermal-oxidative aging (RTFOT, temperature 163 °C, aging time 5 h) and ultraviolet accelerated aging test (UV, ultraviolet light intensity 1200 μW / cm 2 , temperature 60 °C, aging time 9 days); then test the properties of each sample before and after aging, and calculate 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%). The test results are shown in Table 1.

[0148] Table 1: Test results of the anti-aging performance of the modified asphalts prepared in Examples 1-5 and Comparative Examples 1-5

[0149]

[0150] As can be seen from Table 1, compared with Example 1, in Comparative Example 1, SBS was directly used to modify asphalt. After the modified asphalt underwent thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rates were significantly lower than those of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt of the present invention, while the softening point increment was much greater than that of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt of the present invention. Compared with Example 1, in Comparative Example 2, IRMOF-1-Cu(II) was directly used to modify asphalt. After the modified asphalt underwent thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rates were significantly lower than those of the anti-aging IRMOF-1-Cu(II) modified asphalt of the present invention, while the softening point increment was significantly greater than that of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt of the present invention. Compared with Example 1, in Comparative Example 3, IRMOF-1-defect / SBS was used to modify asphalt. After the modified asphalt underwent thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rates were significantly lower than those of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt of the present invention, while the softening point increment was much greater than that of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt of the present invention. The above results show that the modified asphalt prepared by the IRMOF-1-Cu(II) / SBS modifier of the present invention has more excellent thermal-oxidative aging and ultraviolet aging resistance performance compared with the asphalt modified directly with SBS or directly with IRMOF-1-Cu(II) or modified with IRMOF-1-defect / SBS.

[0151] Compared with Example 1, in Comparative Example 4, a relatively small amount of IRMOF-1-Cu(II) / SBS modifier was used to modify asphalt. After the modified asphalt underwent thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rates were significantly lower than those of the modified asphalt prepared in the present invention, while the softening point increment was much greater than that of the anti-aging IRMOF-1-Cu(II) / SBS modified asphalt of the present invention; compared with Example 1, in Comparative Example 5, a large amount of IRMOF-1-Cu(II) / SBS modifier was used to modify asphalt. After the modified asphalt underwent thermal-oxidative aging and ultraviolet aging, its residual penetration and ductility retention rates were significantly lower than those of the modified asphalt prepared in the present invention, while the softening point increment was significantly greater than that of the modified asphalt prepared in the present invention; the above results show that using too little or too much IRMOF-1-Cu(II) / SBS modifier to modify asphalt will not achieve ideal effects. Only when the dosage of the IRMOF-1-Cu(II) / SBS modifier is controlled within the scope of the present invention can a modified asphalt with excellent thermal-oxidative aging and ultraviolet aging resistance performance be obtained.

[0152] In summary, the present invention prepares IRMOF-1-Cu(II) by regulating the structure of IRMOF-1, introducing defect sites, and modifying the structural defects with single-atom metal Cu(II). The composite modifier prepared based on IRMOF-1-Cu(II) according to the present invention can efficiently store aromatic components, thereby achieving the effect of inhibiting its gelation. Moreover, IRMOF-1-Cu(II) has good compatibility and stability with SBS, can synergistically enhance the modification effect of the composite modifier, and further significantly improve the anti-aging performance of asphalt.

[0153] The above specific embodiments have described the implementation of the present invention in detail. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the claims and technical concept of the present invention, various simple modifications and changes can be made to the technical solution of the present invention, and these simple variations all belong to the protection scope of the present invention.

Claims

1. An IRMOF-1-Cu(II) / SBS composite modifier, characterized in that By mass fraction, it includes the following raw materials: 27% - 37% of IRMOF-1-Cu(II), 52% - 60% of SBS, 0.2% - 0.4% of accelerator, and 10.8% - 14.6% of compatibilizer; Among them, the preparation method of the IRMOF-1-Cu(II) includes the following steps: S1. Mix soluble zinc salt, terephthalic acid, monocarboxylic acid and solvent evenly, and react at 100 - 150 °C; Centrifuge to collect the precipitate product, wash and dry it to obtain the defective metal-organic framework IRMOF-1 crystal, denoted as IRMOF-1-defect; S2. Mix IRMOF-1-defect, soluble copper salt and solvent evenly, and react at 80 - 100 °C; Centrifuge to collect the precipitate product and wash it to obtain IRMOF-1-Cu(II).

2. The IRMOF-1-Cu(II) / SBS composite modifier according to claim 1, wherein The molar ratio of the soluble zinc salt to terephthalic acid is 2:1; The mass ratio of terephthalic acid to monocarboxylic acid is 1:(4 - 18).

3. An IRMOF-1-Cu(II) / SBS composite modifier according to claim 1, characterized in that The mass ratio of the IRMOF-1-defect to the soluble copper salt is 1:

1.

4. An IRMOF-1-Cu(II) / SBS composite modifier according to claim 1, characterized in that The soluble zinc salt includes but is not limited to at least one of zinc chloride, zinc nitrate, and zinc acetate; The monocarboxylic acid includes but is not limited to at least one of formic acid, acetic acid, and benzoic acid; The soluble copper salt includes but is not limited to at least one of copper chloride and copper nitrate.

5. An IRMOF-1-Cu(II) / SBS composite modifier according to claim 1, characterized in that The solvent includes but is not limited to at least one of N,N-dimethylformamide, γ-valerolactone, N,N-diethylformamide, and ethanol.

6. The IRMOF-1-Cu(II) / SBS composite modifier according to claim 1, characterized in that, The accelerator includes but is not limited to at least one of tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and bis(1,5-pentamethylene)tetramthiuram disulfide; The compatibilizer includes but is not limited to catalytic slurry.

7. The preparation method of the IRMOF-1-Cu(II) / SBS composite modifier according to any one of claims 1 to 6, characterized in that, It includes the following steps: Mix IRMOF-1-Cu(II), SBS, accelerator and compatibilizer evenly, and granulate to obtain the IRMOF-1-Cu(II) / SBS composite modifier.

8. The application of the IRMOF-1-Cu(II) / SBS composite modifier according to any one of claims 1 - 6 in the preparation of aging-resistant asphalt.

9. An aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt, characterized in that, By mass fraction, it includes the following raw materials: 89.5% - 93.5% of asphalt, 6% - 10% of the IRMOF-1-Cu(II) / SBS composite modifier according to any one of claims 1 - 6, and 0.5% of stabilizer.

10. The preparation method of the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt according to claim 9, characterized in that, It includes the following steps: Heat the asphalt to a flowing state, add the RMOF-1-Cu(II) / SBS composite modifier and stabilizer, keep the temperature at 160 - 180 °C, stir at a speed of 4000 - 6000 rpm for 1 - 3 h; Continue to keep the temperature at 160 - 180 °C, and then continue to stir at a speed of 400 - 600 rpm for 1 - 3 h to obtain the aging-resistant IRMOF-1-Cu(II) / SBS modified asphalt.

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