Preparation method of low-noise water-damage-resistant asphalt mixture
By combining modified basalt porous ceramic hybrid aggregate and self-healing gel modified asphalt material, the problems of asphalt mixture being easily damaged by rainwater infiltration and noise were solved, achieving a comprehensive performance improvement of low noise, water damage resistance and self-healing.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUNAN KUNDA BUILDING MATERIALS CO LTD
- Filing Date
- 2025-06-13
- Publication Date
- 2026-04-28
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Existing asphalt mixtures are prone to water damage under rainwater infiltration, and it is difficult to achieve both low noise and self-healing capabilities, thus failing to meet the comprehensive requirements of modern road engineering for environmental protection, durability and sustainability.
By combining modified basalt porous ceramic hybrid aggregate and self-healing gel modified bitumen material, a porous structure is formed through vacuum sintering, surface activation and polyurethane impregnation. Combined with gel masterbatch with a three-dimensional cross-linked network, low noise, water damage resistance and self-healing functions are achieved.
It significantly improves the water damage resistance and noise reduction properties of asphalt mixtures, extends their service life, and achieves a synergistic effect of low noise, water damage resistance and self-healing.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of asphalt technology, specifically to a method for preparing low-noise, water-damage-resistant asphalt mixtures. Background Technology
[0002] As a key material in road engineering, asphalt mixtures generally face two major technical bottlenecks during long-term service: Firstly, rainwater infiltration reduces the adhesion between aggregates and asphalt, easily leading to water damage and significantly weakening the overall durability of the pavement structure. Secondly, with the acceleration of urbanization, traffic noise problems are becoming increasingly prominent, and the impact of road noise on the environment and residents' health is becoming more and more severe. Although existing technologies have made improvements to address water damage and noise pollution separately, such as by adding anti-stripping agents to enhance interfacial adhesion or using porous aggregates to absorb noise, it is difficult to achieve both simultaneously: while porous aggregates can significantly reduce noise, they are prone to water absorption, increasing the risk of water damage; water damage resistance design usually comes at the cost of porosity and acoustic performance; in addition, asphalt mixtures are prone to microcracks under long-term loads and environmental changes, lacking effective self-healing capabilities, further shortening the service life of the pavement. Based on this, there is an urgent need to propose a new type of asphalt mixture that combines low noise, high water damage resistance, and self-healing function to overcome the shortcomings of existing technologies that cannot simultaneously balance these three aspects of performance, and to meet the comprehensive needs of modern road engineering for environmental protection, durability, and sustainability. Summary of the Invention
[0003] The purpose of this invention is to provide a low-noise, water-damage-resistant asphalt mixture and its preparation method, so as to solve the problems existing in the prior art.
[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a low-noise water-damage resistant asphalt mixture, wherein the low-noise water-damage resistant asphalt mixture is composed of 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 basalt ore after treatment, introducing carbon dioxide in the middle and late stages of sintering, then activating and soaking the surface with coupling agent, vacuum impregnating with polyurethane liquid, and adding fine aggregates and fillers.
[0006] Furthermore, the self-healing gel-modified asphalt material is prepared by oxygenating tris(2-mercaptoethyl) cyanurate combined with glycerol triglycidyl ether to obtain a gel masterbatch composite asphalt.
[0007] Furthermore, the tri(2-mercaptoethyl) cyanurate is prepared by reacting phosphorus oxychloride with cyanuric acid and preparing trichlorocyanuric acid by vacuum distillation, followed by nucleophilic substitution reaction with 2-(acetylmercapto)ethyl dichlorophosphate to obtain tri(2-acetylmercaptoethyl) cyanurate, and then reducing the acetylmercapto group.
[0008] Furthermore, the 2-(acetylmercapto)ethyl dichlorophosphate is prepared by dissolving 2-mercaptoethanol in anhydrous reagent, adding acetyl chloride dropwise, followed by vacuum distillation, adding anhydrous reagent, and then adding phosphorus oxychloride dropwise in an ice bath.
[0009] Furthermore, a low-noise, water-damage-resistant asphalt mixture includes the following preparation steps: (1) Using 100 parts of basalt ore as the matrix, first crush it to 100-200 mesh, add 3-8 parts of foaming agent and 5-12 parts of fluxing agent and dry mix evenly, sinter in a vacuum environment at 900-1000℃ for 1-2 hours, raise the temperature to 1000-1100℃ in the middle of sintering and introduce 1-3L / min of carbon dioxide to regenerate the oxide into carbonate, continue to keep warm for 2-3 hours; then raise the temperature to 1100-1200℃ and react for 2-3 hours; after cooling, sieve 2-3mm particles to make porous basalt ceramics; (2) Soak porous basalt ceramics in 10-20% dilute hydrochloric acid for 30-60 min to dissolve surface metal oxides, wash with deionized water until neutral, then dry at 60℃ to expose hydroxyl groups, and irradiate with argon atmosphere plasma for 1-3 min to obtain pre-modified porous basalt ceramics. (3) Polyurethane prepolymer was prepared by polymerization of polyether polyol and isocyanate under nitrogen protection; 1-3 parts of coupling agent were mixed with premodified basalt porous ceramic particles and soaked for 1-2 hours; 10-30 parts of polyurethane prepolymer were added to it and mixed and degassed; it was maintained under vacuum for 30-50 minutes; finally, it was cured at gradient temperature to obtain modified basalt porous ceramic; 20-30 parts of fine aggregate and 8-10 parts of filler were 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 were mixed and reacted at 80-100℃ for 3-5h. After the reaction was completed, excess phosphorus oxychloride was recovered by vacuum distillation and trichlorocyanuric acid was obtained. 400 parts of anhydrous THF were added and then 210 parts of 2-(acetylmercapto)ethyl dichlorophosphate were added in sequence. The mixture was stirred at 60-80℃ for 6-8h. After the reaction was completed, inorganic salts were removed by filtration and the filtrate was concentrated and evaporated to obtain tri(2-acetylmercaptoethyl) cyanurate. 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT were added. 40 parts of sodium borohydride were added in batches under an ice bath at 0-5℃. The mixture was then raised to room temperature and reacted for 2-3h. The reaction solution was acidified to neutral and then extracted with 300-400 parts of ethyl acetate. The organic phase was washed and dried to obtain tri(2-mercaptoethyl) cyanurate. (5) Dissolve tris(2-mercaptoethyl) cyanurate in 200 parts THF, add 140 parts glycerol triglycidyl ether and 8 parts catalyst, continuously introduce oxygen at 0.5-1 L / min, react at 60-80℃ for 4-6 h, evaporate the solvent after the reaction to obtain self-healing gel masterbatch; add to matrix asphalt and mix to obtain self-healing gel modified asphalt material; (6) Take 90-95 parts of modified basalt porous ceramic hybrid aggregate, 6-10 parts of self-healing gel modified asphalt material, add anti-stripping agent, mix and heat to 100-120℃ and stir for 1-3 hours to obtain asphalt mixture.
[0010] Furthermore, in step (1), the foaming agent refers to one of calcium carbonate, dolomite, and manganese dioxide; the co-solvent refers to one of potassium feldspar, calcium feldspar, and spodumene.
[0011] Furthermore, in step (2), the amount of dilute hydrochloric acid used is 6-10 times the volume of the ceramic particles.
[0012] Furthermore, the coupling agent in step (3) refers to one of KH-550, KH-560 and KH-835.
[0013] Furthermore, in step (3), gradient curing refers to curing at 60-100℃ for 1 hour first, and then heating to 80-120℃ for 2 hours.
[0014] Furthermore, in step (3), the fine aggregate and filler 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 to 0-5°C in an ice bath, adding dropwise a mixture of 85 parts of acetyl chloride and 95 parts of pyridine, heating to 25°C and stirring for 2 hours after titration, removing the solvent by vacuum evaporation, adding 100 parts of anhydrous THF, adding dropwise 140 parts of phosphorus oxychloride in an ice bath, stirring at 25°C for 1 hour, filtering, and evaporating and concentrating to obtain 2-(acetylmercapto)ethyl dichlorophosphate.
[0016] Furthermore, in step (5), the base bitumen is 8-10 times the mass of the gel masterbatch.
[0017] Furthermore, in step (6), the anti-stripping agent is AD-here LOF65-00, and the amount added is 0.2-0.6% of the total mass of the self-healing gel modified asphalt.
[0018] Compared with the prior art, the beneficial effects achieved by the present invention are: The asphalt mixture prepared by this invention includes modified basalt porous ceramic aggregate and self-healing gel modified asphalt material to achieve the effects of low noise, water damage resistance and heat insulation. First, basalt ore is used as raw material. After crushing, grinding, granulation, and molding, it is mixed with a flux and foaming agent for segmented sintering. Vacuum sintering is carried out in the early stage. After sintering, carbon dioxide gas is introduced to continue sintering at a high temperature. The pore structure is optimized by gas phase control. Temporary carbonates are formed by gas-solid reaction with components such as calcium oxide and magnesium oxide. The subsequent temperature increase decomposes the carbonates, increasing the porosity of the material. After cooling and sieving, the sintered product is used to obtain porous basalt ceramic particles. After surface activation treatment, after soaking in coupling agent, a vacuum-assisted impregnation process is used to fully fill the ceramic pores with polyurethane solution. After drying and crosslinking, a continuous polymer film layer with hydrophobic modification is formed, and hybrid aggregate is prepared to modify asphalt. This achieves sound wave dissipation and noise reduction of porous structure, resulting in low noise effect and hydrophobic surface resistance to water damage.
[0019] Secondly, under nitrogen protection, trichlorocyanuric acid was prepared by reacting phosphorus oxychloride with cyanuric acid and then by vacuum distillation. This trichlorocyanuric acid was subsequently subjected to a nucleophilic substitution reaction with 2-(acetylmercapto)ethyl dichlorophosphate: tris(2-acetylmercaptoethyl)cyanurate was formed through nitrogen-carbon-oxygen bond construction, and the acetylmercapto group was reduced to obtain tris(2-mercaptoethyl)cyanurate. Further, an appropriate amount of oxygen was introduced, and glycerol triglycidyl ether was introduced to undergo an epoxy-mercapto-sulfhydryl reaction to generate thioether bonds, forming a three-dimensional cross-linked network under the action of a catalyst. The gel masterbatch; the three-dimensional rigid structure of the cyanuric acid core provides mechanical support; the thiol group is oxidized into dynamic disulfide bonds, giving the material self-healing properties; after the gel masterbatch is combined with asphalt, the three-dimensional network structure not only enhances the material's resistance to water damage, but its multi-scale porous 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 microcracks occur 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 asphalt. Detailed Implementation
[0020] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0021] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The testing methods for various indicators of a low-noise, water-damage-resistant asphalt mixture prepared in the following embodiments are as follows: Low noise performance: The low noise performance of the asphalt mixtures prepared in the examples and comparative examples was determined 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 determined in accordance with the provisions of "JTG / F40-2004 Technical Specification for Construction of Highway Asphalt Pavement".
[0023] Example 1 (1) Using 100 parts of basalt ore as the matrix, after crushing to 100 mesh, add 3 parts of calcium carbonate foaming agent and 5 parts of potassium feldspar flux, and dry mix evenly at a stirring speed of 300 rpm, under a vacuum of 10 -1 The oxide was sintered at 900℃ for 1 hour in a vacuum environment of Pa; then the temperature was raised to 1000℃ and carbon dioxide was introduced at 1L / min to regenerate the oxide into carbonate, and the temperature was maintained for 2 hours; then the temperature was raised to 1100℃ and reacted for 2 hours. After cooling, 2 mm particles were sieved to obtain porous basalt ceramics. (2) Soak porous basalt ceramic particles in 10wt% dilute hydrochloric acid for 30 min and stir at a low speed of 200 rpm to dissolve the surface metal oxides. The amount of dilute hydrochloric acid used is 6 times the volume of ceramic. Then wash with deionized water until neutral, dry at 60℃ for 2 h to expose hydroxyl groups, and irradiate with plasma at 5 kV and 12 mA for 1 min under argon atmosphere to obtain pre-modified porous basalt ceramic. (3) Polyurethane prepolymer was prepared by polymerizing 100 parts of polyether polyol and 25 parts of isocyanate at 60°C with medium speed of 300 rpm for 3 h under nitrogen protection; 1 part of silane coupling agent KH-560 was prepared into 1 wt% ethanol solution and mixed with 60 parts of premodified ceramic particles at 200 rpm for 1 h of soaking treatment; 10 parts of polyurethane prepolymer were added and mixed at high speed of 500 rpm for degassing, and then vacuum-0.1 MPa was maintained for 30 min for gradient curing: first cured at 60°C for 1 h, and then heated to 80°C for 2 h to obtain 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 modified basalt porous ceramic hybrid aggregate; (4) In this step, under nitrogen protection, 100 parts of cyanuric acid and 260 parts of phosphorus oxychloride were stirred at 80°C for 3 hours at a stirring speed of 100 rpm and a pressure of 3.5 kPa to recover excess phosphorus oxychloride by vacuum distillation to obtain material A; 400 parts of anhydrous THF were added to material A, and then 70 parts of material D were added in three batches every 15 minutes, and the mixture was stirred at 60°C at a medium speed of 300 rpm for 6 hours. After filtering to remove inorganic salts, the mixture was evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material B; then 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 in an ice bath at 0°C, and the mixture was stirred at room temperature at a medium speed of 300 rpm for 2 hours. After h, the reaction solution was acidified to neutral with anhydrous THF and extracted with 300 parts of ethyl acetate. The organic phase was washed with saturated brine, dried with anhydrous sodium sulfate, and then evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material C. In this process, 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 titration, the temperature was raised to 25°C and stirred at 300 rpm for 2 h. The solvent was removed by vacuum distillation at 1.5 kPa, and 100 parts of anhydrous THF were added. 140 parts of phosphorus oxychloride were added dropwise in an ice bath at 0°C, and the mixture was stirred at 300 rpm for 1 h at 25°C. The mixture was then filtered, evaporated, and concentrated 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 glycerol triglycidyl ether and 8 parts of triethylamine, continuously introduce oxygen at 0.5 L / min, and react at 60°C for 4 h; after evaporating at 80°C for 4 h to obtain self-healing gel masterbatch, add 8 times the mass of the gel masterbatch of Shell No. 70 asphalt and stir at 120°C at 500 rpm for 2 h to obtain self-healing gel modified asphalt material; (6) Take 90 parts of modified basalt porous ceramic hybrid aggregate and 6 parts of self-healing gel modified asphalt, add 0.2% AD-here LOF65-00 anti-stripping agent of the total mass of self-healing gel modified asphalt, heat to 100℃, and stir at 500rpm for 1h to obtain asphalt mixture.
[0024] Example 2 (1) Using 100 parts of basalt ore as the matrix, after crushing to 150 mesh, add 5 parts of dolomite foaming agent and 8 parts of anorthite fluxing agent, and dry mix evenly at a stirring speed of 300 rpm, under a vacuum of 10 -1 The oxide was sintered at 950℃ for 1.5h in a vacuum environment of Pa; then the temperature was raised to 1050℃ and carbon dioxide was introduced at 2L / min to regenerate the oxide into carbonate, and the temperature was maintained for another 2.5h; then the temperature was raised to 1150℃ and reacted for 2.5h. After cooling, 2.5mm particles were sieved to obtain porous basalt ceramics. (2) The porous basalt ceramic particles were soaked in 15wt% dilute hydrochloric acid for 45 min with a volume of 8 times that of the ceramic particles and stirred at a low speed of 200 rpm to dissolve the surface metal oxides. They were washed with deionized water until neutral, dried at 60℃ for 2 h to expose the hydroxyl groups, and then irradiated with plasma at a voltage of 5 kV and a current of 12 mA for 2 min under an argon atmosphere to obtain pre-modified porous basalt ceramics. (3) Polyurethane prepolymer was prepared by polymerizing 100 parts of polyether polyol and 25 parts of isocyanate at 60°C with medium speed of 300 rpm for 3 h under nitrogen protection; 2 parts of silane coupling agent KH-550 were prepared into 2wt% ethanol solution and mixed with 60 parts of premodified ceramic particles at 200 rpm for 1.5 h of soaking treatment; 20 parts of polyurethane prepolymer were added and mixed at high speed of 500 rpm for degassing, and then the mixture was maintained under vacuum of -0.1 MPa for 40 min and then gradient cured: first cured at 80°C for 1 h, and then heated to 100°C for 2 h to obtain 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 modified basalt porous ceramic hybrid aggregate; (4) In this step, under nitrogen protection, 100 parts of cyanuric acid and 300 parts of phosphorus oxychloride were stirred at 90°C for 4 hours at a stirring speed of 100 rpm and a pressure of 3.5 kPa to distill off excess phosphorus oxychloride to obtain material A; 400 parts of anhydrous THF were added to material A, and then 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. After filtering to remove inorganic salts, the mixture was evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material B; then 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT were added. The mixture was then stirred in an ice bath at 0°C in two batches every 15 minutes for 2 hours at a medium speed of 300 rpm. After 5 hours, the reaction solution was acidified to neutral with anhydrous THF and extracted with 350 parts of ethyl acetate. The organic phase was washed with saturated brine, dried with anhydrous sodium sulfate, and then evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material C. In this process, 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 titration, the temperature was raised to 25°C and stirred at 300 rpm for 2 hours. The solvent was removed by vacuum distillation at 1.5 kPa, and 100 parts of anhydrous THF were added. 140 parts of phosphorus oxychloride were added dropwise in an ice bath at 0°C, and the mixture was stirred at 300 rpm for 1 hour in an ice bath at 25°C. The mixture was then filtered, evaporated, and concentrated 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 glycerol triglycidyl ether and 8 parts of triethylamine, continuously introduce oxygen at 0.8 L / min, and react at 70°C for 5 h; after evaporating at 80°C for 4 h to obtain self-healing gel masterbatch, add 9 times the mass of the gel masterbatch of Shell No. 70 asphalt and stir at 120°C at 500 rpm for 2 h to obtain self-healing gel modified asphalt material; (6) Take 93 parts of modified basalt porous ceramic hybrid aggregate and 8 parts of self-healing gel modified asphalt, add 0.4% AD-here LOF65-00 anti-stripping agent of the total mass of self-healing gel modified asphalt, heat to 110℃, stir at 500rpm for 2h to obtain asphalt mixture.
[0025] Example 3 (1) Using 100 parts of basalt ore as the matrix, after crushing to 200 mesh, add 8 parts of manganese dioxide foaming agent and 12 parts of spodumene flux and dry mix evenly at a stirring speed of 300 rpm, under a vacuum of 10 -1 The oxide was sintered at 1000℃ for 2 hours in a vacuum environment of Pa; then the temperature was raised to 1100℃ and carbon dioxide was introduced at 3L / min to regenerate the oxide into carbonate, and the temperature was maintained for another 3 hours; then the temperature was raised to 1200℃ and reacted for 3 hours. After cooling, 3mm particles were sieved to obtain porous basalt ceramics. (2) The porous basalt ceramic particles were soaked in 20wt% dilute hydrochloric acid for 60 min with a volume of 10 times that of the ceramic particles and stirred at a low speed of 200 rpm to dissolve the surface metal oxides. They were washed with deionized water until neutral, dried at 60℃ 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 under an argon atmosphere to obtain pre-modified porous basalt ceramics. (3) Polyurethane prepolymer was prepared by polymerizing 100 parts of polyether polyol and 25 parts of isocyanate at 60°C with medium speed of 300 rpm for 3 h under nitrogen protection; 2 parts of silane coupling agent KH-835 were prepared into a 3wt% ethanol solution and mixed with 60 parts of premodified ceramic particles at a stirring speed of 200 rpm for 2 h; 30 parts of polyurethane prepolymer were added and mixed at high speed of 500 rpm to remove bubbles, and then the mixture was maintained under vacuum of -0.1 MPa for 50 min and then gradient cured: first cured at 100°C for 1 h, and then heated to 120°C for 2 h to obtain 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 modified basalt porous ceramic hybrid aggregate; (4) In this step, under nitrogen protection, 100 parts of cyanuric acid and 340 parts of phosphorus oxychloride were stirred at 100°C for 5 hours at a stirring speed of 100 rpm and a pressure of 3.5 kPa to recover excess phosphorus oxychloride by vacuum distillation to obtain material A; 400 parts of anhydrous THF were added to material A, and then 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. After filtering to remove inorganic salts, the mixture was evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material B; then 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 in an ice bath at 0°C. The mixture was stirred at room temperature at a medium speed of 300 rpm. After 3 hours, the reaction solution was acidified to neutral with anhydrous THF and extracted with 400 parts of ethyl acetate. The organic phase was washed with saturated brine, dried with anhydrous sodium sulfate, and then evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material C. In this process, 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 titration, the temperature was raised to 25°C and stirred at 300 rpm for 2 hours. The solvent was removed by vacuum distillation at 1.5 kPa, and 100 parts of anhydrous THF were added. 140 parts of phosphorus oxychloride were added dropwise in an ice bath at 0°C, and the mixture was stirred at 300 rpm for 1 hour in a medium-speed environment at 25°C. The mixture was then filtered, evaporated, and concentrated 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 glycerol triglycidyl ether and 8 parts of triethylamine, continuously introduce oxygen at 1L / min, and react at 80℃ for 6h; after evaporating at 80℃ for 4h to obtain self-healing gel masterbatch, add 10 times the mass of the gel masterbatch of Shell No. 70 asphalt and stir at 120℃ at 500rpm for 2h to obtain self-healing gel modified asphalt material; (6) Take 95 parts of modified basalt porous ceramic hybrid aggregate and 10 parts of self-healing gel modified asphalt, add 0.6% AD-here LOF65-00 anti-stripping agent of the total mass of self-healing gel modified asphalt, heat to 120℃, and stir at 500rpm for 3h to obtain asphalt mixture.
[0026] Comparative Example 1 The difference between Comparative Example 1 and Example 2 lies in step (1). Step (1) is changed to: using 100 parts of basalt ore as the matrix, crushing it to 150 mesh, adding 5 parts of dolomite foaming agent and 8 parts of anorthite co-solvent, and dry mixing evenly at a stirring speed of 300 rpm, under a vacuum of 10 -1 The ceramic was sintered at 950°C for 1 hour in a vacuum environment of Pa; then the temperature was raised to 1050°C and held for 2.5 hours; then the temperature was raised to 1150°C and reacted for 2.5 hours. After cooling, 2.5 mm particles were sieved to obtain porous basalt ceramics; the remaining steps were the same as in Example 2.
[0027] Comparative Example 2 The difference between Comparative Example 2 and Example 2 lies in step (3). Step (3) is changed to: under nitrogen protection, 100 parts of polyether polyol and 25 parts of isocyanate are stirred at 300 rpm at 60°C for 3 hours to produce 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 200 rpm, and soaked for 1.5 hours to obtain modified basalt porous ceramic; finally, 20 parts of machine-made basalt sand and 8 parts of lime powder are added to the modified basalt porous ceramic and mixed to obtain 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 different steps (4), (5), and (6). Steps (4), (5), and (6) are changed to: (4) In this step, under nitrogen protection, 100 parts of cyanuric acid and 300 parts of phosphorus oxychloride are stirred at 90°C for 4 hours at a stirring speed of 100 rpm and a pressure of 3.5 kPa to recover excess phosphorus oxychloride by vacuum distillation to obtain material A; 400 parts of anhydrous THF are added to material A, and then 70 parts of material D are added in three batches every 15 minutes, and stirred at 60°C at a medium speed of 300 rpm for 7 hours. After removing inorganic salts by filtration, the solution is evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material B. Specifically, under nitrogen protection, 100 parts of 2-mercaptoethanol are dissolved in 200 parts of anhydrous THF, and a mixture of 85 parts of acetyl chloride and 95 parts of pyridine is added dropwise in an ice bath at 0°C. After titration, the temperature is raised to 25°C and stirred at 300 rpm for 2 hours. The solvent is removed by vacuum distillation at 1.5 kPa, and 100 parts of anhydrous THF are added. 140 parts of phosphorus oxychloride are added dropwise in an ice bath at 0°C, and the mixture is stirred at 300 rpm for 1 hour at 25°C. The solution is then filtered, evaporated, and concentrated to 1 / 3 of the original filtrate volume to obtain material D. (5) Dissolve 100 parts of material B in 200 parts of THF, add 140 parts of glycerol triglycidyl ether and 8 parts of triethylamine, continuously introduce oxygen at 0.8 L / min, and react at 70°C for 5 h; after evaporating at 80°C for 4 h to obtain masterbatch, add 9 times the mass of Shell No. 70 asphalt and stir at 120°C at 500 rpm for 2 h to obtain modified asphalt material; (6) Take 93 parts of modified basalt porous ceramic hybrid aggregate and 8 parts of modified asphalt, add 0.4% AD-here LOF65-00 anti-stripping agent of the total mass of modified asphalt, heat to 110℃, stir at 500rpm for 2h to obtain asphalt mixture; the remaining steps are 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) Dissolve 100 parts of material C in 200 parts of THF, continuously introduce oxygen at 0.8 L / min, and react at 70°C for 5 h; after evaporating at 80°C for 4 h to obtain masterbatch, add 9 times the mass of Shell No. 70 asphalt and stir at 120°C at 500 rpm for 2 h to obtain modified asphalt material; (6) Take 93 parts of modified basalt porous ceramic hybrid aggregate and 8 parts of modified asphalt, add 0.4% AD-here LOF65-00 anti-stripping agent of the total mass of modified asphalt, heat to 110℃, stir at 500rpm for 2h to obtain asphalt mixture; the remaining steps are the same as in Example 2.
[0030] Example of effect Table 1 below shows the performance analysis results of a low-noise, water-damage-resistant asphalt mixture using Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention.
[0031] Table 1 A comparison of the water immersion residual stability and noise decibel experimental data from the examples and comparative examples reveals that this invention significantly improves the water damage resistance and noise reduction characteristics of asphalt mixtures through the innovative treatment of the porous basalt ceramic matrix, the composite reinforcement of aggregates, and the combined effect of self-healing gel-modified asphalt. First, the basalt ore is subjected to specific particle size reduction, foaming agent / flux ratio adjustment, and vacuum gradient sintering, followed by the introduction of carbon dioxide to regenerate the oxides into carbonates. This activation process optimizes the ceramic pore structure and surface activity. Second, after acid washing and plasma activation pretreatment, the porous ceramic is composite impregnated and gradient cured using a silane coupling agent and polyurethane prepolymer, and then hybridized with manufactured sand and lime powder, significantly enhancing the interfacial bonding force, structural integrity, and water damage resistance of the aggregates. Finally, tris(2-mercaptoethyl) cyanurate containing active mercapto groups is synthesized through a multi-step reaction, and further condensed with glycerol in an oxygen atmosphere. A thiol-epoxy click chemical reaction occurs between water-glycerol ether and a thiol, forming a cross-linked network structure to obtain a self-healing gel masterbatch, which is then uniformly dispersed in the base asphalt. It can be seen that in the experimental scheme, aggregates account for the majority of the composition. Omitting the carbon dioxide activation step will lead to deterioration of ceramic properties, reduced porosity, and decreased water immersion resistance and sound insulation. Omitting polyurethane composite modification will severely weaken the aggregate strengthening effect, resulting in a significant decrease in water immersion resistance and noise reduction performance. If the reduction of active thiol groups is not completed or the gel network construction is omitted, the self-healing function will significantly fail, and the overall performance of the mixture will decrease. However, the asphalt mixture that fully implements this scheme achieves a synergistic improvement in water damage resistance and low noise performance due to the sound absorption and noise reduction effect of the activated ceramics, the strengthened aggregate skeleton support and anti-stripping properties, and the self-healing ability of the gel network cracks. Among these, the process parameter combination represented by Example 2 exhibits the optimal balance of overall performance.
[0032] 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 implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.
Claims
1. A method for preparing a low-noise, water-damage-resistant asphalt mixture, characterized in that, The preparation steps include the following: (1) Using 100 parts of basalt ore as the matrix, after crushing to 150 mesh, add 5 parts of dolomite foaming agent and 8 parts of anorthite fluxing agent, and dry mix evenly at a stirring speed of 300 rpm, under a vacuum of 10 -1 The oxide was sintered at 950℃ for 1.5h in a vacuum environment of Pa; then the temperature was raised to 1050℃ and carbon dioxide was introduced at 2L / min to regenerate the oxide into carbonate, and the temperature was maintained for another 2.5h; then the temperature was raised to 1150℃ and reacted for 2.5h. After cooling, 2.5mm particles were sieved to obtain porous basalt ceramics. (2) The porous basalt ceramic particles were soaked in 15wt% dilute hydrochloric acid for 45 min with a volume of 8 times that of the ceramic particles and stirred at a low speed of 200 rpm to dissolve the surface metal oxides. The particles were washed with deionized water until neutral and dried at 60°C for 2 h to expose the hydroxyl groups. The particles were then irradiated with plasma at a voltage of 5 kV and a current of 12 mA for 2 min under an argon atmosphere to obtain pre-modified porous basalt ceramics. (3) Polyurethane prepolymer was prepared by polymerizing 100 parts of polyether polyol and 25 parts of isocyanate at 60°C with medium speed of 300 rpm for 3 h under nitrogen protection; 2 parts of silane coupling agent KH-550 were prepared into 2wt% ethanol solution and mixed with 60 parts of premodified ceramic particles at 200 rpm for 1.5 h of soaking treatment; 20 parts of polyurethane prepolymer were added and mixed at high speed of 500 rpm for degassing, and then the mixture was maintained under vacuum of -0.1 MPa for 40 min and then gradient cured: first cured at 80°C for 1 h, and then heated to 100°C for 2 h to obtain 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 modified basalt porous ceramic hybrid aggregate; (4) In this step, under nitrogen protection, 100 parts of cyanuric acid and 300 parts of phosphorus oxychloride were stirred at 90°C for 4 hours at a stirring speed of 100 rpm and a pressure of 3.5 kPa to distill off excess phosphorus oxychloride to obtain material A; 400 parts of anhydrous THF were added to material A, and then 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. After filtering to remove inorganic salts, the mixture was evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material B; then 300 parts of anhydrous methanol, 180 parts of potassium carbonate and 1 part of BHT were added. The mixture was then stirred in an ice bath at 0°C in two batches every 15 minutes for 2 hours at a medium speed of 300 rpm. After 5 hours, the reaction solution was acidified to neutral with anhydrous THF and extracted with 350 parts of ethyl acetate. The organic phase was washed with saturated brine, dried with anhydrous sodium sulfate, and then evaporated and concentrated to 1 / 3 of the original filtrate volume to obtain material C. In this process, 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 titration, the temperature was raised to 25°C and stirred at 300 rpm for 2 hours. The solvent was removed by vacuum distillation at 1.5 kPa, and 100 parts of anhydrous THF were added. 140 parts of phosphorus oxychloride were added dropwise in an ice bath at 0°C, and the mixture was stirred at 300 rpm for 1 hour in an ice bath at 25°C. The mixture was then filtered, evaporated, and concentrated 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 glycerol triglycidyl ether and 8 parts of triethylamine, continuously introduce oxygen at 0.8 L / min, and react at 70°C for 5 h; after evaporating at 80°C for 4 h to obtain self-healing gel masterbatch, add 9 times the mass of the gel masterbatch of Shell No. 70 asphalt and stir at 120°C at 500 rpm for 2 h to obtain self-healing gel modified asphalt material; (6) Take 93 parts of modified basalt porous ceramic hybrid aggregate and 8 parts of self-healing gel modified asphalt, add 0.4% AD-here LOF65-00 anti-stripping agent of the total mass of self-healing gel modified asphalt, heat to 110℃, stir at 500rpm for 2h to obtain asphalt mixture.