Low-noise water-damage-resistant asphalt mixture and preparation method thereof

Abstract

The invention discloses a low-noise water-damage-resistant asphalt mixture and a preparation method thereof, and relates to the technical field of asphalt. The mixture is formed by compounding a modified basalt porous ceramic hybrid aggregate and a self-repairing gel modified asphalt material, wherein the modified basalt porous ceramic hybrid aggregate is prepared by crushing basalt ore, introducing carbon dioxide in vacuum gradient sintering to optimize a pore structure under the synergistic effect of a foaming agent and a cosolvent, and then mixing the aggregate and a filler through acid pickling, plasma activation and polyurethane impregnation reinforcement; according to the self-repairing gel modified asphalt, tris (2-mercaptoethyl) cyanurate is used as a precursor, a cross-linked gel network is formed through a thiol-epoxy click chemical reaction, and then the cross-linked gel network is compounded with matrix asphalt; according to the scheme, through the synergistic effect of sound wave dissipation of the porous ceramic and dynamic self-repairing of a hydrophobic interface and a gel network, the water damage resistance and noise reduction performance of the mixture are remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of asphalt, in particular to a low-noise and water-damage-resistant asphalt mixture and a preparation method thereof. Background Art

[0002] Asphalt mixtures, a key material in road construction, face two common technical bottlenecks during long-term service. First, rainwater infiltration reduces aggregate-asphalt interfacial adhesion, leading to water damage and significantly reducing the overall durability of the pavement structure. Second, with the acceleration of urbanization, traffic noise is becoming increasingly prominent, and the impact of road noise on the environment and residents' health is becoming increasingly severe. While existing technologies have addressed both water damage and noise pollution, such as by adding anti-stripping agents to enhance interfacial adhesion or using porous aggregates to absorb noise, achieving both simultaneously is difficult. While porous aggregates can significantly reduce noise, they readily absorb water, increasing the risk of water damage. Water damage resistance often comes at the expense of porosity and acoustic performance. Furthermore, asphalt mixtures are prone to microcracks under long-term loads and environmental changes, lacking effective self-healing capabilities, further shortening the pavement's service life. Consequently, there is an urgent need to develop a new asphalt mixture that combines low noise, high water damage resistance, and self-healing capabilities to overcome the existing inability to simultaneously balance these three performance aspects and meet the comprehensive requirements of modern road construction for environmental protection, durability, and sustainability. Summary of the Invention

[0003] The purpose of the present invention is to provide a low-noise and water-damage-resistant asphalt mixture and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: a low-noise and water-damage-resistant asphalt mixture, which is formed by mixing modified basalt porous ceramic hybrid aggregate and self-healing gel modified asphalt material.

[0005] Furthermore, the modified basalt porous ceramic hybrid aggregate is prepared by vacuum sintering the treated basalt ore and introducing carbon dioxide in the middle and late stages of sintering, then activating the surface of the basalt ore, soaking it in a coupling agent, vacuum impregnating it with polyurethane liquid, and adding fine aggregate and filler to mix.

[0006] Furthermore, the self-repairing gel-modified asphalt material is prepared by oxygenating tris(2-mercaptoethyl)cyanurate and propylene glycol triglycidyl ether to obtain a gel masterbatch composite asphalt.

[0007] Furthermore, the tris(2-mercaptoethyl)cyanurate is prepared by reacting phosphorus oxychloride with cyanuric acid and preparing cyanuric acid trichloroate by reduced pressure distillation, followed by a nucleophilic substitution reaction with 2-(acetylmercapto)ethyl dichlorophosphate to obtain tris(2-acetylmercaptoethyl)cyanurate and reducing the acetylmercapto group.

[0008] Furthermore, the 2-(acetylmercapto)ethyl dichlorophosphate is prepared by dissolving 2-mercaptoethanol in an anhydrous reagent, adding acetyl chloride dropwise, and then distilling under reduced pressure, then adding an anhydrous reagent and adding phosphorus oxychloride dropwise in an ice bath.

[0009] Furthermore, a low-noise, water-damage-resistant asphalt mixture comprises the following preparation steps: (1) 100 parts of basalt ore are used as the matrix, first crushed to 100-200 mesh, added with 3-8 parts of foaming agent and 5-12 parts of auxiliary solvent, dry-mixed evenly, sintered at 900-1000℃ in a vacuum environment for 1-2 hours, heated to 1000-1100℃ in the middle of sintering and introduced with 1-3L / min of carbon dioxide to regenerate the oxide into carbonate, and kept warm for 2-3 hours; then heated to 1100-1200℃ and reacted for 2-3 hours; after cooling, 2-3mm particles were sieved to obtain porous basalt ceramics; (2) adding 10-20% by mass of dilute hydrochloric acid to soak the porous basalt ceramics for 30-60 minutes to dissolve the surface metal oxides, washing with deionized water until neutral, then drying at 60°C to expose the hydroxyl groups, and irradiating with argon atmosphere plasma for 1-3 minutes to obtain pre-modified basalt porous ceramics; (3) Polyurethane prepolymer is prepared by polymerization of polyether polyol and isocyanate under nitrogen protection; 1-3 parts of coupling agent are mixed with pre-modified basalt porous ceramic particles and soaked for 1-2 hours; 10-30 parts of polyurethane prepolymer are added thereto and continued to mix and degas; the mixture is maintained under vacuum for 30-50 minutes; and finally, gradient temperature curing is performed to obtain modified basalt porous ceramics; 20-30 parts of fine aggregate and 8-10 parts of filler are added to obtain modified basalt porous ceramic hybrid aggregate; (4) Under nitrogen protection, 100 parts of cyanuric acid and 260-340 parts of phosphorus oxychloride are mixed and reacted at 80-100°C for 3-5 hours. After the reaction is completed, the excess phosphorus oxychloride is recovered by vacuum distillation to obtain trichlorocyanuric acid; 400 parts of anhydrous THF are added and then 210 parts of 2-(acetylmercapto)ethyl dichlorophosphate are added in sequence, and the mixture is stirred and reacted at 60-80°C for 6-8 hours. After the reaction is completed, the inorganic salt is filtered to remove the inorganic salt, and the filtrate is concentrated and evaporated to obtain tris(2-acetylmercaptoethyl)cyanurate; 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT are added, and 40 parts of sodium borohydride are added in batches at 0-5°C ice bath, and then the mixture is heated to room temperature for 2-3 hours. The reaction solution is acidified to neutrality and extracted with 300-400 parts of ethyl acetate. The organic phase is washed and dried to obtain tris(2-mercaptoethyl)cyanurate; (5) Dissolve tris(2-mercaptoethyl)cyanurate in 200 parts of THF, add 140 parts of propylene glycol triglycidyl ether and 8 parts of a catalyst, continuously introduce 0.5-1 L / min of oxygen, react at 60-80°C for 4-6 hours, evaporate and remove the solvent after the reaction to obtain a self-healing gel masterbatch; add the matrix asphalt and mix to obtain a self-healing gel modified asphalt material; (6) Take 90-95 parts of modified basalt porous ceramic hybrid aggregate, 6-10 parts of self-repairing gel modified asphalt material, add anti-stripping agent, mix, heat to 100-120℃, stir and react for 1-3 hours to prepare asphalt mixture.

[0010] Furthermore, in step (1), the foaming agent is one of calcium carbonate, dolomite and manganese dioxide; and the solvent is one of potassium feldspar, calcium feldspar and spodumene.

[0011] Furthermore, the amount of dilute hydrochloric acid used in step (2) is 6-10 times the volume of the ceramic particles.

[0012] Furthermore, the coupling agent in step (3) is one of KH-550, KH-560 and KH-835.

[0013] Furthermore, the gradient curing in step (3) refers to curing at 60-100°C for 1 hour and then heating to 80-120°C for curing for 2 hours.

[0014] Furthermore, the fine aggregate and filler in step (3) refer to machine-made basalt sand and lime powder, respectively.

[0015] Furthermore, in step (4), 2-(acetylmercapto)ethyl dichlorophosphate is prepared by dissolving 100 parts of 2-mercaptoethanol in 200 parts of anhydrous THF under nitrogen protection, cooling the mixture to 0-5°C in an ice bath, adding dropwise a mixture of 85 parts of acetyl chloride and 95 parts of pyridine, heating the mixture to 25°C after titration, stirring for 2h, removing the solvent by evaporation under reduced pressure, adding 100 parts of anhydrous THF, adding dropwise 140 parts of phosphorus oxychloride in an ice bath, stirring at 25°C for 1h, filtering, and concentrating by evaporation to obtain 2-(acetylmercapto)ethyl dichlorophosphate.

[0016] Furthermore, in step (5), the mass of the matrix asphalt is 8-10 times that of the gel masterbatch.

[0017] Furthermore, the anti-stripping agent in step (6) is AD-here LOF65-00, and the added amount is 0.2-0.6% of the total mass of the self-repairing gel-modified asphalt.

[0018] Compared with the prior art, the present invention has the following beneficial effects: The asphalt mixture prepared by the present invention includes modified basalt porous ceramic aggregate and self-repairing gel modified asphalt material to achieve low noise, water damage resistance and thermal insulation effects; Firstly, basalt ore is used as raw material, which is crushed, ground, granulated and formed, and then mixed with a solvent and a foaming agent for segmented sintering: vacuum sintering is carried out in the early stage, and carbon dioxide gas is introduced after sintering to continue sintering at a constant temperature. The pore structure is optimized through gas phase regulation, and a temporary carbonate is formed by gas-solid reaction with calcium oxide, magnesium oxide and other components, which is then decomposed by increasing the temperature to increase the porosity of the material; the sintered product is cooled and screened to obtain porous basalt ceramic particles, which are then surface activated and soaked in a coupling agent. The polyurethane solution is fully filled into the ceramic pores using a vacuum-assisted impregnation process, and a continuous polymer film layer with surface hydrophobic modification is formed after drying and cross-linking, thereby preparing a hybrid aggregate with modified asphalt; the sound wave dissipation noise reduction of the porous structure is achieved, achieving a low noise effect and surface hydrophobic and water damage resistance.

[0019] Secondly, under nitrogen protection, trichlorocyanurate is prepared by reacting phosphorus oxychloride with cyanuric acid and distilling under reduced pressure, and then undergoes a nucleophilic substitution reaction with 2-(acetylmercapto)ethyl dichlorophosphate: tris(2-acetylmercaptoethyl)cyanurate is formed through a nitrogen-carbon-oxygen bond, and tris(2-mercaptoethyl)cyanurate is obtained by reducing the acetylmercapto group; further, an appropriate amount of oxygen is introduced and glycerol triglycidyl ether is introduced to react with epoxy-mercapto groups to generate thioether bonds, and a three-dimensional cross-linked network is formed under the action of a catalyst. The three-dimensional rigid structure of the cyanuric acid core provides mechanical support; the thiol part is oxidized into dynamic disulfide bonds, giving the material self-healing properties; after the gel masterbatch is compounded with asphalt, the three-dimensional network structure not only enhances the material's resistance to water damage, but its multi-scale pore structure can also form a synergistic noise reduction effect with modified basalt porous ceramics, and also has a certain thermal insulation capacity; and when the material is subjected to external force or micro-cracks due to temperature changes, the dynamic disulfide bonds can break and rearrange to achieve self-repair of the damaged area, thereby significantly extending the service life of the asphalt. DETAILED DESCRIPTION

[0020] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0021] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of a low-noise, water-damage-resistant asphalt mixture prepared in the following examples. Low noise performance: The low noise performance of the asphalt mixtures prepared in the examples and comparative examples was measured in accordance with the provisions of GB / T 21396-2008 Road Traffic Noise Measurement Method.

[0022] Water damage resistance: The water damage resistance of the asphalt mixtures prepared in the examples and comparative examples was measured in accordance with the provisions of JTG / F40-2004 Technical Specifications for Highway Asphalt Pavement Construction. Example 1

[0023] (1) Take 100 parts of basalt ore as the matrix, crush it to 100 mesh, add 3 parts of calcium carbonate foaming agent and 5 parts of potassium feldspar solvent, stir at 300 rpm and dry mix evenly. -1 Pa vacuum environment at 900 ° C for 1 hour; then the temperature was raised to 1000 ° C and 1 L / min of carbon dioxide was introduced to regenerate the oxide into carbonate, and the temperature was kept for another 2 hours; then the temperature was raised to 1100 ° C for 2 hours, and after cooling, 2 mm particles were sieved to obtain porous basalt ceramics; (2) The porous basalt ceramic particles were soaked in 10 wt% dilute hydrochloric acid for 30 min and stirred at a low speed of 200 rpm to dissolve the surface metal oxides. The amount of dilute hydrochloric acid used was 6 times the volume of the ceramic. The particles were then washed with deionized water until neutral, dried at 60 °C for 2 h to expose the hydroxyl groups, and irradiated with plasma at a voltage of 5 kV and a current of 12 mA for 1 min in an argon atmosphere to obtain pre-modified porous basalt ceramics. (3) Under nitrogen protection, 100 parts of polyether polyol and 25 parts of isocyanate were stirred at 300 rpm at 60 ° C for 3 hours to obtain a polyurethane prepolymer; 1 part of silane coupling agent KH-560 was prepared into a 1wt% ethanol solution and mixed with 60 parts of pre-modified ceramic particles at a stirring speed of 200 rpm and soaked for 1 hour; 10 parts of polyurethane prepolymer were added and mixed at a high speed of 500 rpm for degassing, and vacuum -0.1 MPa was maintained for 30 minutes and then gradient cured: first cured at 60 ° C for 1 hour, then heated to 80 ° C for 2 hours to obtain a modified basalt porous ceramic; finally, 20 parts of machine-made basalt sand and 8 parts of lime powder were added to the modified basalt porous ceramic to obtain a modified basalt porous ceramic hybrid aggregate; (4) In this step, 100 parts of cyanuric acid and 260 parts of phosphorus oxychloride were stirred and reacted at 80°C for 3 hours under nitrogen protection, with a stirring speed of 100 rpm and a pressure of 3.5 KPa. Excess phosphorus oxychloride was recovered by reduced pressure distillation to obtain material A; 400 parts of anhydrous THF were added to material A, and 70 parts of material D were added in three batches every 15 minutes. The mixture was stirred at 60°C at a medium speed of 300 rpm for 6 hours. The inorganic salt was filtered and concentrated by evaporation to 1 / 3 of the original filtrate volume to obtain material B; 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT were added, and 20 parts of sodium borohydride were added in two batches every 15 minutes at room temperature at a medium speed of 300 rpm to react for 2 hours. h later, the reaction solution was acidified to neutrality with anhydrous THF and extracted with 300 parts of ethyl acetate, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to 1 / 3 of the original filtrate volume to obtain material C; wherein, 100 parts of 2-mercaptoethanol were dissolved in 200 parts of anhydrous THF under nitrogen protection, and a mixture of 85 parts of acetyl chloride and 95 parts of pyridine was added dropwise in an ice bath at 0°C. After the titration was completed, the temperature was raised to 25°C and stirred at a medium speed of 300 rpm for 2h; after the solvent was removed by distillation under reduced pressure at 1.5 KPa, 100 parts of anhydrous THF were added, 140 parts of phosphorus oxychloride were added dropwise in an ice bath at 0°C, stirred at a medium speed of 300 rpm at 25°C for 1h, filtered and evaporated to 1 / 3 of the original filtrate volume to obtain material D; (5) Dissolve 100 parts of material C in 200 parts of THF, add 140 parts of propylene glycol triglycidyl ether and 8 parts of triethylamine, continuously introduce 0.5 L / min of oxygen, and react at 60 ° C for 4 hours; evaporate at 80 ° C for 4 hours to obtain a self-healing gel masterbatch, add 8 times the mass of the gel masterbatch Shell No. 70 asphalt and stir at 120 ° C at 500 rpm for 2 hours to obtain a self-healing gel modified asphalt material; (6) 90 parts of modified basalt porous ceramic hybrid aggregate were mixed with 6 parts of self-healing gel-modified asphalt, and 0.2% AD-here LOF65-00 anti-stripping agent of the total mass of the self-healing gel-modified asphalt was added. The mixture was heated to 100 °C and stirred at 500 rpm for 1 h to prepare an asphalt mixture. Example 2

[0024] (1) Take 100 parts of basalt ore as the matrix, crush it to 150 mesh, add 5 parts of dolomite foaming agent and 8 parts of anorthite solvent, stir at 300 rpm and dry mix evenly, under vacuum degree of 10 -1 The sintering was carried out at 950°C in a vacuum environment of 1.5 hours. The temperature was then raised to 1050°C and 2L / min of carbon dioxide was introduced to regenerate the oxide into carbonate, and the temperature was kept at this temperature for another 2.5 hours. The temperature was then raised to 1150°C for reaction for 2.5 hours. After cooling, 2.5mm particles were sieved to obtain porous basalt ceramics. (2) The porous basalt ceramic particles were soaked in 15 wt% dilute hydrochloric acid (8 times the volume of the ceramic) for 45 min and stirred at a low speed of 200 rpm to dissolve the surface metal oxides. The particles were washed with deionized water until neutral, dried at 60 °C for 2 h to expose the hydroxyl groups, and irradiated with plasma at a voltage of 5 kV and a current of 12 mA in an argon atmosphere for 2 min to obtain pre-modified basalt porous ceramics. (3) Under nitrogen protection, 100 parts of polyether polyol and 25 parts of isocyanate were stirred at 300 rpm at 60 ° C for 3 hours to obtain a polyurethane prepolymer; 2 parts of silane coupling agent KH-550 were prepared into a 2wt% ethanol solution and mixed with 60 parts of pre-modified ceramic particles at a stirring speed of 200 rpm, and soaked for 1.5 hours; 20 parts of polyurethane prepolymer were added and mixed at a high speed of 500 rpm for degassing, and vacuum -0.1 MPa was maintained for 40 minutes and then gradient cured: first cured at 80 ° C for 1 hour, then heated to 100 ° C for 2 hours to obtain a modified basalt porous ceramic; finally, 20 parts of machine-made basalt sand and 8 parts of lime powder were added to the modified basalt porous ceramic, and mixed to obtain a modified basalt porous ceramic hybrid aggregate; (4) In this step, 100 parts of cyanuric acid and 300 parts of phosphorus oxychloride were stirred and reacted at 90°C for 4 hours under nitrogen protection, with a stirring speed of 100 rpm and a pressure of 3.5 kPa. Excess phosphorus oxychloride was recovered by reduced pressure distillation to obtain material A; 400 parts of anhydrous THF were added to material A, and 70 parts of material D were added in three batches every 15 minutes. The mixture was stirred at 60°C at a medium speed of 300 rpm for 7 hours. The inorganic salt was filtered and concentrated by evaporation to 1 / 3 of the original filtrate volume to obtain material B; 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT were added, and 20 parts of sodium borohydride were added in two batches every 15 minutes at room temperature at a medium speed of 300 rpm to react for 2 hours. After 5 hours, the reaction solution was acidified to neutrality with anhydrous THF and extracted with 350 parts of ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to 1 / 3 of the original filtrate volume to obtain material C; wherein, 100 parts of 2-mercaptoethanol were dissolved in 200 parts of anhydrous THF under nitrogen protection, and a mixture of 85 parts of acetyl chloride and 95 parts of pyridine was added dropwise in an ice bath at 0°C. After the titration was completed, the temperature was raised to 25°C and stirred at a medium speed of 300 rpm for 2 hours; after the solvent was removed by distillation under reduced pressure at 1.5 KPa, 100 parts of anhydrous THF were added, 140 parts of phosphorus oxychloride were added dropwise in an ice bath at 0°C, stirred at a medium speed of 300 rpm at 25°C for 1 hour, and filtered and evaporated to 1 / 3 of the original filtrate volume to obtain material D; (5) Dissolve 100 parts of material C in 200 parts of THF, add 140 parts of propylene glycol triglycidyl ether and 8 parts of triethylamine, continuously introduce 0.8 L / min of oxygen, and react at 70 ° C for 5 h; evaporate at 80 ° C for 4 h to obtain a self-healing gel masterbatch, add 9 times the mass of the gel masterbatch Shell No. 70 asphalt and stir at 120 ° C at a high speed of 500 rpm for 2 h to obtain a self-healing gel modified asphalt material; (6) 93 parts of modified basalt porous ceramic hybrid aggregate were mixed with 8 parts of self-healing gel-modified asphalt, and 0.4% AD-here LOF65-00 anti-stripping agent of the total mass of the self-healing gel-modified asphalt was added. The mixture was heated to 110 °C and stirred at 500 rpm for 2 h to obtain an asphalt mixture. Example 3

[0025] (1) Take 100 parts of basalt ore as the matrix, crush it to 200 mesh, add 8 parts of manganese dioxide foaming agent and 12 parts of spodumene solvent, stir at 300 rpm and dry mix evenly, under vacuum degree of 10 -1 Pa vacuum environment at 1000 ° C for 2 hours; then the temperature was raised to 1100 ° C and 3 L / min of carbon dioxide was introduced to regenerate the oxide into carbonate, and the temperature was kept for another 3 hours; then the temperature was raised to 1200 ° C for 3 hours, and after cooling, 3 mm particles were sieved to obtain porous basalt ceramics; (2) The porous basalt ceramic particles were soaked in 20 wt% dilute hydrochloric acid (10 times the volume of the ceramic) for 60 min and stirred at a low speed of 200 rpm to dissolve the surface metal oxides. The particles were washed with deionized water until neutral, dried at 60 °C for 2 h to expose the hydroxyl groups, and irradiated with plasma at a voltage of 5 kV and a current of 12 mA for 3 min in an argon atmosphere to obtain pre-modified basalt porous ceramics. (3) Under nitrogen protection, 100 parts of polyether polyol and 25 parts of isocyanate were stirred at 300 rpm at 60 ° C for 3 hours to obtain a polyurethane prepolymer; 2 parts of silane coupling agent KH-835 were prepared into a 3wt% ethanol solution and mixed with 60 parts of pre-modified ceramic particles at a stirring speed of 200 rpm and soaked for 2 hours; 30 parts of polyurethane prepolymer were added and mixed at a high speed of 500 rpm for degassing, and vacuum-0.1 MPa was maintained for 50 minutes and then gradient cured: first cured at 100 ° C for 1 hour, then heated to 120 ° C for 2 hours to obtain a modified basalt porous ceramic; finally, 20 parts of machine-made basalt sand and 8 parts of lime powder were added to the modified basalt porous ceramic to obtain a modified basalt porous ceramic hybrid aggregate; (4) In this step, 100 parts of cyanuric acid and 340 parts of phosphorus oxychloride were stirred at 100°C for 5 hours under nitrogen protection, with a stirring speed of 100 rpm and a pressure of 3.5 KPa. Excess phosphorus oxychloride was recovered by vacuum distillation to obtain material A; 400 parts of anhydrous THF were added to material A, and 70 parts of material D were added in three batches every 15 minutes. The mixture was stirred at 60°C and 300 rpm for 7 hours. The inorganic salt was filtered and concentrated by evaporation to 1 / 3 of the original filtrate volume to obtain material B; 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT were added, and 20 parts of sodium borohydride were added in two batches every 15 minutes at room temperature and 300 rpm for reaction. After 3 hours, the reaction solution was acidified to neutrality with anhydrous THF and extracted with 400 parts of ethyl acetate. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and evaporated to 1 / 3 of the original filtrate volume to obtain material C; wherein, 100 parts of 2-mercaptoethanol were dissolved in 200 parts of anhydrous THF under nitrogen protection, and a mixture of 85 parts of acetyl chloride and 95 parts of pyridine was added dropwise in a 0°C ice bath. After the titration was completed, the temperature was raised to 25°C and stirred at a medium speed of 300 rpm for 2 hours; after the solvent was removed by distillation under reduced pressure at 1.5 KPa, 100 parts of anhydrous THF were added, 140 parts of phosphorus oxychloride were added dropwise in a 0°C ice bath, stirred at a medium speed of 300 rpm for 1 hour, and filtered and evaporated to 1 / 3 of the original filtrate volume to obtain material D; (5) Dissolve 100 parts of material C in 200 parts of THF, add 140 parts of propylene glycol triglycidyl ether and 8 parts of triethylamine, continuously introduce 1 L / min of oxygen, and react at 80 ° C for 6 hours; evaporate at 80 ° C for 4 hours to obtain a self-healing gel masterbatch, add 10 times the mass of the gel masterbatch Shell No. 70 asphalt and stir at 120 ° C at 500 rpm for 2 hours to obtain a self-healing gel modified asphalt material; (6) 95 parts of modified basalt porous ceramic hybrid aggregate were mixed with 10 parts of self-healing gel-modified asphalt, and 0.6% AD-here LOF65-00 anti-stripping agent of the total mass of the self-healing gel-modified asphalt was added. The mixture was heated to 120 °C and stirred at 500 rpm for 3 h to obtain an asphalt mixture.

[0026] Comparative Example 1 The difference between Comparative Example 1 and Example 2 lies in the difference in step (1). Step (1) is changed to: 100 parts of basalt ore are used as the matrix, crushed to 150 mesh, 5 parts of dolomite foaming agent and 8 parts of anorthite solvent are added and dry-mixed at a stirring speed of 300 rpm, and the vacuum degree is 10 -1 Pa vacuum environment, sintering at 950 ° C for 1 hour; then heating to 1050 ° C and continuing to heat for 2.5 hours; then heating to 1150 ° C for reaction for 2.5 hours, cooling and screening 2.5 mm particles to obtain porous basalt ceramics; the remaining steps are the same as Example 2.

[0027] Comparative Example 2 The difference between Comparative Example 2 and Example 2 lies in the difference in step (3). Step (3) is changed to: under nitrogen protection, 100 parts of polyether polyol and 25 parts of isocyanate are stirred at a medium speed of 300 rpm at 60°C for 3 hours to polymerize to obtain a polyurethane prepolymer; 2 parts of silane coupling agent KH-550 are prepared into a 2wt% ethanol solution and mixed with 60 parts of pre-modified ceramic particles at a stirring speed of 200 rpm, and soaked for 1.5 hours to obtain modified basalt porous ceramics; finally, 20 parts of machine-made basalt sand and 8 parts of lime powder are added to the modified basalt porous ceramics, and the mixture is mixed to obtain a modified basalt porous ceramic hybrid aggregate; the remaining steps are the same as in Example 2.

[0028] Comparative Example 3 The difference between Comparative Example 3 and Example 2 lies in the difference in steps (4) (5) (6). Steps (4) (5) (6) are changed to: (4) In this step, 100 parts of cyanuric acid and 300 parts of phosphorus oxychloride are stirred and reacted at 90°C for 4h under nitrogen protection, with a stirring speed of 100rpm and a pressure of 3.5KPa. Excess phosphorus oxychloride is recovered by reduced pressure distillation to obtain material A; 400 parts of anhydrous THF are added to material A, and 70 parts of material D are added in three batches every 15min, and the reaction is stirred at 60°C at a medium speed of 300rpm for 7h. After filtering out the inorganic salts, the mixture was evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material B; wherein, 100 parts of 2-mercaptoethanol were dissolved in 200 parts of anhydrous THF under nitrogen protection, and a mixture of 85 parts of acetyl chloride and 95 parts of pyridine was added dropwise in an ice bath at 0°C. After the titration was completed, the temperature was raised to 25°C and stirred at a medium speed of 300 rpm for 2h; after the solvent was removed by distillation under reduced pressure at 1.5KPa, 100 parts of anhydrous THF were added, 140 parts of phosphorus oxychloride were added dropwise in an ice bath at 0°C, stirred at a medium speed of 300 rpm at 25°C for 1h, and filtered and evaporated to 1 / 3 of the original filtrate volume to obtain material D; 100 parts of material B were dissolved in 200 parts of THF, 140 parts of glycerol triglycidyl ether and 8 parts of triethylamine were added, and oxygen was continuously introduced at 0.8 L / min. The mixture was reacted at 70°C for 5 hours. After evaporation at 80°C for 4 hours to obtain a masterbatch, 9 times the mass of the masterbatch was added to Shell No. 70 asphalt, and the mixture was stirred at 120°C at 500 rpm for 2 hours to obtain a modified asphalt material. 93 parts of modified basalt porous ceramic hybrid aggregate were mixed with 8 parts of modified asphalt, 0.4% AD-here LOF65-00 anti-stripping agent based on the total mass of the modified asphalt was added, the temperature was raised to 110°C, and the mixture was stirred at 500 rpm for 2 hours to prepare an asphalt mixture; the remaining steps were the same as in Example 2.

[0029] Comparative Example 4 The difference between Comparative Example 4 and Example 2 lies in the difference in steps (5) and (6). Steps (5) and (6) are changed to: (5) 100 parts of material C are dissolved in 200 parts of THF, 0.8 L / min of oxygen is continuously introduced, and the mixture is reacted at 70°C for 5 h; after evaporation at 80°C for 4 h to obtain a masterbatch, 9 times the mass of the masterbatch of Shell No. 70 asphalt is added and stirred at 120°C at a high speed of 500 rpm for 2 h to obtain a modified asphalt material; (6) 93 parts of modified basalt porous ceramic hybrid aggregate were mixed with 8 parts of modified asphalt, and 0.4% AD-here LOF65-00 anti-stripping agent was added based on the total mass of the modified asphalt. The mixture was heated to 110°C and stirred at 500 rpm for 2 h to obtain an asphalt mixture. The remaining steps were the same as those in Example 2.

[0030] Effect Examples Table 1 below shows the performance analysis results of a low-noise, water-damage-resistant asphalt mixture using Examples 1 to 3 of the present invention and Comparative Examples 1 to 4.

[0031] Table 1

[0032] From the comparison of the experimental data of the residual stability and noise decibel of the embodiment and the comparative example, it can be found that the present invention significantly improves the water damage resistance and noise reduction characteristics of the asphalt mixture through the innovative treatment of the porous basalt ceramic matrix, the composite reinforcement of the aggregate and the combined effect of the self-healing gel modified asphalt; First, the basalt ore is subjected to a specific crushing particle size, a foaming agent / flux ratio and vacuum gradient sintering, and carbon dioxide is introduced to regenerate the oxide into carbonate. This activation process optimizes the pore structure and surface activity of the ceramic; Second, after pickling and plasma activation pretreatment, the porous ceramic is compositely impregnated and gradient cured with a silane coupling agent and a polyurethane prepolymer, and then hybridized with machine-made sand and lime powder, which greatly enhances the interface bonding force, structural integrity and water damage resistance of the aggregate; Finally, tris(2-mercaptoethyl)cyanurate containing active thiol groups is synthesized through a multi-step reaction, and further reacted with propylene glycol tris(2-mercaptoethyl)cyanurate in an oxygen atmosphere. Glyceryl ether undergoes a thiol-epoxy click chemical reaction to form a cross-linked network structure to produce a gel masterbatch with self-repairing function, which is then evenly dispersed in the matrix asphalt. It can be seen that in the experimental scheme, aggregate accounts for the vast majority. If the carbon dioxide activation step is omitted, the ceramic performance will be deteriorated, the porosity will be reduced, and the water immersion resistance and sound insulation effect will be reduced. Omitting the polyurethane composite modification will seriously weaken the aggregate strengthening effect, and the water immersion resistance and noise reduction performance will be seriously reduced. If the reduction of the active thiol group is not completed or the gel network construction is omitted, the self-repairing function will be significantly invalidated and the comprehensive performance of the mixture will be reduced. The asphalt mixture that fully implements this scheme has achieved a synergistic improvement in water damage resistance and low noise due to the sound absorption and noise reduction effect of the activated ceramic, the skeleton support and anti-peeling property of the strengthened aggregate, and the crack self-healing ability of the gel network. Among them, the process parameter combination represented by Example 2 shows the best comprehensive performance balance.

[0033] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be encompassed therein. Any reference in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A low-noise, water-damage-resistant asphalt mixture, which is made by mixing modified basalt porous ceramic hybrid aggregate and self-repairing gel-modified asphalt material, characterized in that: The modified basalt porous ceramic hybrid aggregate is prepared by vacuum sintering basalt ore after treatment, introducing carbon dioxide in the middle and late stages of sintering, activating the surface of the basalt ore, soaking it in a coupling agent, vacuum impregnating it with polyurethane liquid, and adding fine aggregate and filler to mix. The self-repairing gel-modified asphalt material is prepared by oxygenating tris(2-mercaptoethyl)cyanurate and glycerol triglycidyl ether to obtain a gel masterbatch composite asphalt.

2. The low-noise and water-damage-resistant asphalt mixture according to claim 1, characterized in that: The method comprises the following preparation steps: (1) 100 parts of basalt ore are used as the matrix, first crushed to 100-200 mesh, added with 3-8 parts of foaming agent and 5-12 parts of solvent, dry-mixed evenly, sintered at 900-1000℃ in a vacuum environment for 1-2 hours, and after sintering, heated to 1000-1100℃ and introduced with 1-3L / min of carbon dioxide to regenerate the oxide into carbonate, and then heated for 2-3 hours; then heated to 1100-1200℃ and reacted for 2-3 hours; after cooling, 2-3mm particles were sieved to obtain porous basalt ceramics; (2) adding a 10-20% by mass aqueous solution of dilute hydrochloric acid to soak the porous basalt ceramics for 30-60 minutes to dissolve the surface metal oxides, washing with deionized water until neutral, then drying at 60°C to expose the hydroxyl groups, and irradiating with argon atmosphere plasma for 1-3 minutes to obtain pre-modified basalt porous ceramics; (3) Polyether polyol and isocyanate are polymerized to prepare a polyurethane prepolymer under nitrogen protection; 1-3 parts of a coupling agent are prepared into a solution and then mixed with the pre-modified basalt porous ceramic particles, and then immersed for 1-2 hours; 10-30 parts of the polyurethane prepolymer are then added thereto and mixed and degassed continuously, and degassed under vacuum conditions for 30-50 minutes; after degassed, the mixture is cured at a gradient temperature to obtain a modified basalt porous ceramic; 20-30 parts of fine aggregate and 8-10 parts of filler are then added to obtain a modified basalt porous ceramic hybrid aggregate; (4) Under nitrogen protection, 100 parts of cyanuric acid and 260-340 parts of phosphorus oxychloride are mixed and reacted at 80-100°C for 3-5 hours. After the reaction is completed, the excess phosphorus oxychloride is recovered by vacuum distillation to obtain trichlorocyanuric acid; 400 parts of anhydrous THF are added and then 210 parts of 2-(acetylmercapto)ethyl dichlorophosphate are added in sequence, and the mixture is stirred and reacted at 60-80°C for 6-8 hours. After the reaction is completed, the inorganic salt is filtered to remove the inorganic salt, and the filtrate is concentrated and evaporated to obtain tris(2-acetylmercaptoethyl)cyanurate; 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT are added, and 40 parts of sodium borohydride are added in batches at 0-5°C ice bath, and then the mixture is heated to room temperature for 2-3 hours. The reaction solution is acidified to neutrality and extracted with 300-400 parts of ethyl acetate. The organic phase is washed and dried to obtain tris(2-mercaptoethyl)cyanurate; (5) Dissolve tris(2-mercaptoethyl)cyanurate in 200 parts of THF, add 140 parts of propylene glycol triglycidyl ether and 8 parts of a catalyst, continuously introduce 0.5-1 L / min of oxygen, react at 60-80°C for 4-6 hours, evaporate and remove the solvent after the reaction to obtain a self-healing gel masterbatch; add the matrix asphalt and mix to obtain a self-healing gel modified asphalt material; (6) Take 90-95 parts of modified basalt porous ceramic hybrid aggregate, 6-10 parts of self-repairing gel modified asphalt material, add anti-stripping agent, mix, heat to 100-120℃, stir and react for 1-3 hours to prepare asphalt mixture.

3. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: In the step (1), the foaming agent is one of calcium carbonate, dolomite and manganese dioxide; and the solvent is one of potassium feldspar, calcium feldspar and spodumene.

4. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: In step (2), the amount of dilute hydrochloric acid aqueous solution used is 6-10 times the volume of the ceramic particles.

5. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: The coupling agent in step (3) is one of KH-550, KH-560 and KH-835.

6. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: The gradient curing in step (3) refers to curing at 60-100°C for 1 hour and then heating to 80-120°C for curing for 2 hours.

7. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: In step (3), the fine aggregate and filler refer to machine-made basalt sand and lime powder, respectively.

8. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: In the step (4), 2-(acetylmercapto)ethyl dichlorophosphate is prepared by dissolving 100 parts of 2-mercaptoethanol in 200 parts of anhydrous THF under nitrogen protection, cooling the mixture to 0-5°C in an ice bath, adding dropwise a mixture of 85 parts of acetyl chloride and 95 parts of pyridine, heating the mixture to 25°C after titration and stirring for 2h, removing the solvent by evaporation under reduced pressure, adding 100 parts of anhydrous THF, adding dropwise 140 parts of phosphorus oxychloride in an ice bath, stirring at 25°C for 1h, filtering, and concentrating by evaporation to obtain 2-(acetylmercapto)ethyl dichlorophosphate.

9. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: In step (5), the mass of the matrix asphalt is 8-10 times that of the gel masterbatch.

10. The low-noise and water-damage-resistant asphalt mixture according to claim 2, characterized in that: The anti-stripping agent in step (6) is AD-here LOF65-00, and the added amount is 0.2-0.6% of the total mass of the self-repairing gel-modified asphalt.

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