Asphalt mixtures and methods for making the same

Abstract

The application discloses asphalt mixture and a preparation method thereof. The asphalt mixture comprises the following components in parts by weight: graded stone: 92.5-95.8 parts; environment-friendly asphalt: 4-6 parts; odor-free temperature control microcapsule: 0.2-1.5 parts; the odor-free temperature control microcapsule comprises a composite shell material and a core material, wherein the composite shell material comprises an inorganic base shell, barium titanate nanoparticles, polydopamine and cuprous oxide, the core material comprises n-alkane with a phase transition temperature of 40-60 DEG C, and the composite shell material is loaded with an active smoke suppression compound. Compared with common asphalt mixture, the asphalt mixture has lower asphalt smoke emission and stronger road performance.

Description

Technical Field

[0001] This invention belongs to the field of special asphalt, specifically relating to a low-odor, temperature-controlled asphalt mixture and its preparation method. Background Technology

[0002] Asphalt mixtures are a key component of transportation infrastructure; however, the traditional hot-mix hot-paving construction process is accompanied by significant asphalt fume emissions. During high-temperature processing, asphalt undergoes complex chemical reactions under the influence of high temperatures and air, generating various malodorous gases and large amounts of low-molecular-weight volatile organic compounds, which pollute the environment and pose a threat to the health of construction workers.

[0003] To address this challenge, extensive research and practice have been conducted globally, particularly in developed countries, on asphalt fume pollution control, accumulating valuable experience. Various treatment technologies have been developed abroad, including combustion, electrostatic precipitation, adsorption, and absorption methods, each with its unique advantages and limitations. For example, combustion offers high efficiency but consumes a lot of energy, electrostatic precipitation requires sophisticated equipment and involves significant investment, while adsorption and absorption methods seek a balance between purification efficiency and system resistance.

[0004] In China, with increasing environmental awareness and stricter air quality standards, higher requirements have been placed on controlling asphalt fume emissions. The government has also introduced stricter emission standards and encouraged the research and application of environmentally friendly asphalt mixtures. Therefore, developing modified asphalt materials that can reduce asphalt fume generation without affecting the performance of asphalt mixtures has become a top priority.

[0005] CN114573283B discloses an environmentally friendly odor-neutralizing asphalt mixture and its preparation method. This method reduces the smoke from the asphalt mixture by adding a liquid odor-neutralizing agent to the asphalt system. However, the odor-neutralizing agent added by this method is relatively simple and has a low boiling point. It is easy to fail during the high-temperature mixing process of the mixture, thereby reducing the smoke suppression effect of the mixture during road construction.

[0006] Therefore, researchers are dedicated to developing novel smoke suppressants to reduce asphalt smoke generation at its source by adding them to asphalt. However, directly adding substances such as activated carbon and hydroxide flame retardants as smoke suppressants may damage the performance of asphalt. Therefore, it is essential to develop a class of smoke suppressants that do not significantly affect the performance of asphalt mixtures.

[0007] In addition, researchers are constantly exploring new solutions to the problems of rutting, sludge, and bleeding that asphalt roads are prone to during service due to high temperatures. These solutions include adding phase change materials to improve the heat absorption properties of asphalt or developing high-performance asphalt materials that are more resistant to high temperatures and have greater durability. However, these materials cannot handle the asphalt fumes generated during the high-temperature construction and mixing process. Summary of the Invention

[0008] To address the problems existing in the prior art, this invention provides an asphalt mixture and its preparation method. Compared with ordinary asphalt mixtures, the asphalt mixture of this invention not only has a lower asphalt fume emission but also has stronger road performance, providing a brand-new approach for the long service life and environmentally friendly utilization of asphalt mixtures.

[0009] The first aspect of this invention provides an asphalt mixture, comprising the following components by weight:

[0010] Graded stone: 92.5-95.8 parts per unit area;

[0011] Environmentally friendly asphalt: 4-6 parts;

[0012] Odor-neutralizing and temperature-controlled microcapsules: 0.2-1.5 parts, preferably 0.4-1.0 parts;

[0013] The odor-neutralizing and temperature-controlled microcapsule comprises a composite shell and a core material. The composite shell comprises an inorganic base shell, barium titanate nanoparticles, polydopamine, and cuprous oxide. The core material comprises n-alkanes with a phase transition temperature of 40-60°C. The surface of the composite shell is loaded with an active smoke-suppressing compound.

[0014] Furthermore, the graded aggregate is one or more of the asphalt mixture gradations AC-10, AC-13, AC-16, AC-20 or SMA-19, SMA-16, SMA-13, SMA-10 that meet the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement".

[0015] Furthermore, the environmentally friendly asphalt, by weight, comprises the following components:

[0016] Odor-neutralizing active ingredient: 0.05-10 parts;

[0017] Dispersant: 1-20 parts;

[0018] Silane coupling agent: 0.1-10 parts;

[0019] Ether compounds: 0.1-10 parts;

[0020] Styrene-butadiene-styrene polymer: 1-20 parts;

[0021] Ethylene-vinyl acetate copolymer: 1-20 parts;

[0022] Base bitumen: 50-500 parts.

[0023] Furthermore, the odor-neutralizing active ingredient is selected from one or more of the following: imide compounds with more than 9 carbon atoms, antioxidants with more than 14 carbon atoms, and aromatic amino compounds with more than 10 carbon atoms.

[0024] Furthermore, the imide compound having more than 9 carbon atoms is selected from one or more of N-phenylmaleimide, N-(4-aminophenyl)maleimide, 4-maleimide-based phenol, and 1-(2-methylphenyl)-1H-pyrrole-2,5-dione.

[0025] Further, the antioxidant with more than 14 carbon atoms is a hindered phenolic antioxidant and / or a phosphite antioxidant. The hindered phenolic antioxidant is selected from one or more of 2,6-di-tert-butyl-p-methylphenol, tert-butylhydroquinone, 2-tert-butyl-p-cresol, 6-tert-butyl-m-cresol, 2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol, and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol). The phosphite antioxidant is selected from one or more of tris(nonylphenol) phosphite, tris(2-cyclohexylphenyl) phosphite, and pentaerythritol distearate diphosphite.

[0026] Furthermore, the aromatic amino compound having more than 10 carbon atoms is selected from one or more of 4-diethylaminobenzaldehyde, 4-(diethylamino)salicylaldehyde, 4-diethylaminobenzaldehyde oxime, 4-(diethylamino)benzaldehyde-1,1-diphenylhydrazone, p-(dipropylamino)benzaldehyde, N,N-diethyl-p-aminobenzaldehyde, and 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde.

[0027] Furthermore, the dispersant is one or more of the following: extracted oil, furfural refined oil, and catalytic cracking slurry.

[0028] Furthermore, the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0029] Furthermore, the ether compound is selected from polyoxyethylene ether compounds containing at least one benzene ring in the molecular chain, preferably selected from one or more of octylphenol polyoxyethylene ether, dinonylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and dodecylphenol polyoxyethylene ether.

[0030] Furthermore, the styrene-butadiene-styrene copolymer is linear and / or star-shaped, with an average relative molecular mass of 100,000 to 300,000.

[0031] Furthermore, in the ethylene-vinyl acetate copolymer, the mass content of vinyl acetate is 20wt% to 30wt% based on the mass of the ethylene-vinyl acetate copolymer.

[0032] Furthermore, the penetration of the base asphalt at 25°C is 30-210 1 / 10 mm.

[0033] Furthermore, the particle size of the odor-neutralizing and temperature-controlled microcapsules is 1-12 μm.

[0034] Furthermore, the mass ratio of the composite shell material to the core material of the odor-neutralizing and temperature-controlled microcapsule is 1:(0.2-2).

[0035] Further, the composite shell material comprises an inorganic base shell / barium titanate nanoparticles / polydopamine / cuprous oxide, wherein the mass ratio of the inorganic base shell to the barium titanate nanoparticles is 1:(0.2-0.8), the mass ratio of the inorganic base shell to the polydopamine is 1:(0.1-0.5), and the mass ratio of the inorganic base shell to the cuprous oxide is 1:(0.5-2).

[0036] Furthermore, the inorganic base shell is made of at least one material selected from silicon dioxide and titanium dioxide, preferably silicon dioxide.

[0037] Furthermore, the n-alkane with a phase transition temperature of 40-60°C is one or more of n-octadecane, n-eicosane, and n-docosahexadecane, preferably n-docosahexadecane.

[0038] Furthermore, the active smoke-suppressing compound is loaded at a rate of 0.1 wt% to 20 wt% of the total mass of the odor-neutralizing and temperature-controlled microcapsules.

[0039] Furthermore, the active smoke-suppressing compound is selected from one or more aldehyde compounds with a molecular weight greater than 160 and / or ketone compounds with a molecular weight greater than 150.

[0040] Furthermore, the aldehyde compound with a molecular weight greater than 160 is selected from one or more of 2-methylundecaldehyde, 10-undecenaldehyde, neojasminealdehyde, citronellol, and citronellol.

[0041] Furthermore, the ketone compound with a molecular weight greater than 150 is selected from one or more of methyl nonyl ketone, geranylacetone, farnesyl acetone, dihydrodamastone, menthone, and allyl ionone.

[0042] A second aspect of the present invention provides a method for preparing the above-mentioned asphalt mixture, comprising:

[0043] a: Preparation of flavor-neutralizing and temperature-controlled microcapsules;

[0044] b: Prepare environmentally friendly asphalt;

[0045] c: Heat the environmentally friendly asphalt obtained in step b to a molten state, mix it with the odor-free and temperature-controlled microcapsules and graded aggregates obtained in step a, and stir to obtain asphalt mixture.

[0046] Further, the method for preparing the odor-neutralizing and temperature-controlled microcapsules in step a includes:

[0047] (1) Preparation of barium titanate nanoparticles;

[0048] (2) Heat the core material raw material to melt, and mix it with solvent and barium titanate nanoparticles obtained in step (1);

[0049] (3) Add the inorganic base shell precursor to the reaction system of step (2), stir and mix to obtain Pickering emulsion;

[0050] (4) Adjust the pH value of the Pickering emulsion, continue stirring, then age, filter, wash, and freeze dry;

[0051] (5) Add the solid material obtained in step (4) to the buffer solution, add dopamine hydrochloride, stir and process, then filter, wash and freeze dry;

[0052] (6) Add the solid particles and copper ion solution obtained in step (5) into the reaction vessel and carry out the reaction with stirring;

[0053] (7) Mix the reducing agent with the buffer solution, stir to dissolve, and then add it to the reaction system of step (6). Stir to carry out the reaction, then filter, wash, and freeze dry.

[0054] (8) Mix the solid particles obtained in step (7) with water, adjust the pH, and then heat and stir; then add silane coupling agent, continue to react under stirring, and then filter, wash and freeze dry.

[0055] (9) The solid material obtained in step (8), the active smoke-suppressing compound, and the strong alkali are added to an organic solvent to react. After cooling, filtering, washing, and freeze-drying, the odor-neutralizing temperature-controlled microcapsules are obtained.

[0056] Furthermore, the method for preparing barium titanate nanoparticles in step (1) includes:

[0057] S1: Stir and mix the titanium precursor and solvent;

[0058] S2: Adjust the pH of the mixed solution obtained in S1 and stir until a titanium precursor sol is obtained;

[0059] S3: Mix the barium precursor with water;

[0060] S4: The titanium precursor sol obtained in S2 is mixed with the mixture obtained in S3 and reacted under stirring. After the reaction is completed, the mixture is filtered, washed, freeze-dried, and ground to obtain primary barium titanate nanoparticles.

[0061] S5: Primary barium titanate nanoparticles, surfactants and solvents are mixed and modified under stirring. After modification, the mixture is washed and freeze-dried to obtain barium titanate nanoparticles.

[0062] Further, in step S1, the titanium precursor is selected from at least one of tetraethyl titanate, n-propyl titanate, and tetrabutyl titanate.

[0063] Further, in step S1, the solvent is an alcohol compound with a boiling point >60°C, and the alcohol compound is an anhydrous alcohol compound, preferably at least one of methanol, butanediol, ethylene glycol, n-butanol, and ethanol.

[0064] Furthermore, in step S1, the stirring temperature is 25-60℃; the stirring speed is 200-500 rpm; and the stirring time is 0.5-3 hours.

[0065] Further, in step S1, the mass ratio of the titanium precursor to the solvent is (1-20):1.

[0066] Further, in step S2, the pH of the S1 mixed solution is adjusted to pH = 9-12.

[0067] Further, in step S2, the pH of the S1 mixed solution is adjusted by adding an alkaline solution dropwise to the S1 solution. The alkaline solution is at least one of ammonia, sodium hydroxide solution, and potassium hydroxide solution.

[0068] Furthermore, in step S2, the stirring temperature is 25-60℃; the stirring speed is 200-500 rpm; and the stirring time is 0.5-3 hours.

[0069] Further, in step S3, the barium precursor is at least one of Ba(OH)2, Ba(OH)2·H2O, and Ba(OH)2·8H2O.

[0070] Further, in step S3, the barium precursor and water are added to the reaction vessel and stirred. The water is deionized water. The mass ratio of the barium precursor to deionized water is (0.5-4):1.

[0071] Furthermore, in step S3, the stirring temperature is 80-120℃; the stirring speed is 200-500 rpm; and the stirring time is 2-5 hours.

[0072] Further, in step S4, the molar ratio of the mixture obtained in S3 (based on barium) to the titanium precursor sol obtained in S2 (based on titanium) is 1:(0.5-5).

[0073] Furthermore, in step S4, the stirring speed is 200-500 rpm; the reaction temperature is 100-200℃; and the reaction time is 2-48 hours.

[0074] Furthermore, in step S4, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0075] Furthermore, in step S4, the grinding specifically means grinding until there are no obvious lumps.

[0076] Furthermore, in step S5, the diameter of the barium titanate nanoparticles is 20-100 nm.

[0077] Further, in step S5, the surfactant is a cationic surfactant, preferably at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride, and more preferably hexadecyltrimethylammonium bromide.

[0078] Further, in step S5, the solvent is an aprotic solvent with a boiling point >100℃, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide.

[0079] Further, in step S5, the mass ratio of the primary barium titanate nanoparticles to the surfactant is 1:(0.1-10), and the mass ratio of the solvent to the primary barium titanate nanoparticles is (5-50):1.

[0080] Furthermore, in step S5, the stirring speed is 200-500 rpm; the modification temperature is 70-180℃; and the modification time is 2-8 hours.

[0081] Furthermore, in step S5, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0082] Furthermore, in step (2), the core material raw material is heated to a melting temperature of 40-80℃.

[0083] Further, in step (2), the solvent is an aprotic solvent with a boiling point >100℃, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0084] Further, in step (2), the mass ratio of the solvent to the barium titanate nanoparticles is (20-80):1.

[0085] Furthermore, in step (2), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

[0086] Further, in step (3), the inorganic base shell precursor is at least one of silicate ester compounds and titanate ester compounds, preferably a silicate ester compound; the silicate ester compound is preferably at least one of methyl silicate, tetraethyl orthosilicate, tetraethyl orthosilicate, and tetraethyl orthosilicate, more preferably tetraethyl orthosilicate.

[0087] Furthermore, in step (3), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

[0088] Further, in step (4), the pH value is adjusted to 3-6. The pH can be adjusted using a dilute acid, such as dilute hydrochloric acid.

[0089] Furthermore, in step (4), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

[0090] Further, in step (4), the aging conditions are: standing at 40-80℃ for 12-30 hours. The freeze-drying conditions are: vacuum drying at -40---20℃ for 4-8 hours.

[0091] Further, in step (5), the buffer solution is one or more of phosphate buffer, carbonate buffer, and tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer), preferably tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer).

[0092] Furthermore, in step (5), the pH value of the buffer solution is preferably 8-10.

[0093] Further, in step (5), the mass ratio of the buffer solution to the solid material obtained in step (4) is (10-100):1.

[0094] Furthermore, in step (5), after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

[0095] Furthermore, in step (5), the stirring speed is 100-300 rpm, the stirring temperature is 20-40℃, and the stirring time is 12-24 hours.

[0096] Furthermore, in step (5), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0097] Further, in step (6), the copper ion solution is prepared by mixing copper ion salt and deionized water, and the copper ion salt is preferably anhydrous copper sulfate.

[0098] Further, in step (6), the concentration of copper ions in the copper ion solution is 0.05-0.5 mol / L.

[0099] Further, in step (6), the mass ratio of the solid particles and copper ion solution obtained in step (5) is 1:(50-200).

[0100] Furthermore, in step (6), the stirring speed is 100-450 rpm, the reaction temperature is 100-190℃, and the reaction time is 1-5 hours.

[0101] Further, in step (7), the reducing agent is a sulfite reducing agent, preferably selected from at least one of potassium sulfite and sodium sulfite.

[0102] Further, in step (7), the buffer solution is selected from one of acetate buffer and phosphate buffer, preferably acetate buffer; the pH value of the buffer solution is 4.5-6.5.

[0103] Further, in step (7), the mass ratio of the reducing agent to the buffer solution is 1:(10-20).

[0104] Furthermore, in step (7), when stirring to dissolve, the stirring speed is 200-450 rpm, the stirring temperature is 40-80℃, and the stirring time is 1-5 hours.

[0105] Furthermore, in step (7), the stirring speed is 100-450 rpm, the reaction temperature is 60-95℃, and the reaction time is 2-5 hours.

[0106] Further, in step (7), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0107] Furthermore, in step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-6h.

[0108] Furthermore, in step (8), the pH is adjusted to 9-11. The pH can be adjusted using a conventional dilute alkaline solution, such as at least one of dilute sodium hydroxide solution or dilute potassium hydroxide solution.

[0109] Further, in step (8), the mass ratio of the solid particles obtained in step (7) to water is 1:(10-50).

[0110] Furthermore, in step (8), the added silane coupling agent is selected from one or more of chloropropyltriethoxysilane, chloromethyltriethoxysilane, dichloromethyltriethoxysilane, and chloromethyltriisopropoxysilane.

[0111] Further, in step (8), the mass ratio of the solid particles obtained in step (7) to the silane coupling agent is 1:(0.5-4).

[0112] Further, in step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-8h.

[0113] Furthermore, the freeze-drying conditions described in step (8) are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0114] Further, in step (9), the organic solvent is selected from one or more of methanol, butanediol, ethylene glycol, n-butanol, and anhydrous ethanol, preferably anhydrous ethanol.

[0115] Further, in step (9), the mass ratio of the solid material obtained in step (8) to the organic solvent is 1:(20-80). The mass ratio of the solid material obtained in step (8) to the strong alkali is 1:(0.5-2).

[0116] Furthermore, in step (9), the strong alkali is either solid KOH or solid NaOH, preferably solid KOH.

[0117] Furthermore, in step (9), the reaction is carried out under reflux and the reaction conditions are: reaction temperature of 80-210℃ and reaction time of 5-10 hours.

[0118] Further, in step (9), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0119] Furthermore, step (b) the method for preparing environmentally friendly asphalt includes:

[0120] I: Heat and stir to mix the odor-neutralizing active ingredient, silane coupling agent, dispersant, and ether compound;

[0121] II: The styrene-butadiene-styrene polymer, ethylene-vinyl acetate copolymer and the mixture obtained in step I are mixed and extruded to obtain asphalt additive;

[0122] III: The asphalt additive obtained in step II is mixed with the molten base asphalt to obtain environmentally friendly asphalt.

[0123] Furthermore, in step I, the stirring speed is 200-500 rpm; the stirring temperature is 30-80℃; and the stirring time is 1-4 hours.

[0124] Furthermore, in step II, the mixing and extrusion can be carried out in a kneader. The mixing conditions are: mixing temperature of 100-160℃, mixing time of 0.5-2h; and extrusion temperature of 100-160℃.

[0125] Furthermore, in step III, the heating temperature for heating the base asphalt to a molten state is 133-153℃. The stirring speed is 400-600 rpm, and the stirring time is 1-4 hours.

[0126] Furthermore, in step c, the environmentally friendly asphalt is heated to a melting temperature of 133℃-163℃.

[0127] Furthermore, in step c, the graded stone is subjected to heat preservation treatment before use. The heat preservation temperature is 160-190℃, and the heat preservation time is 3-5 hours.

[0128] Furthermore, in step c, the mixing conditions are: mixing temperature of 133-163℃ and mixing time of 0.5min-3min.

[0129] Compared with the prior art, the present invention has the following advantages:

[0130] (1) The environmentally friendly asphalt described in this invention, based on the role of silane coupling agent, allows styrene-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, odor-neutralizing active substances and ether compounds to be fused together during the melting and extrusion process to obtain an environmentally friendly high-performance asphalt additive. After being added to asphalt, this environmentally friendly high-performance asphalt additive can not only effectively reduce the amount of harmful asphalt fumes generated during the production and construction process through chemical reaction, but also effectively improve the road performance of asphalt mixtures.

[0131] (2) The composite shell material of the odor-neutralizing and temperature-controlled microcapsule of the present invention includes an inorganic base shell, barium titanate nanoparticles, polydopamine, and cuprous oxide, wherein the barium titanate nanoparticles have multiple functions. Firstly, during the preparation process, the modified barium titanate nanoparticles, due to their nanoscale size, can stably exist between the water and oil interfaces, and can further serve as template agents for microcapsule synthesis, maintaining the stability of the core material mixed droplets. Secondly, under the influence of high temperature, the crystal axis of the barium titanate nanoparticles will be distorted, leading to spontaneous polarization without any external electric field, generating permanent electrodes. On the one hand, during the synthesis of cuprous oxide in the microcapsule composite shell, copper ions can be adsorbed onto the surface of the polydopamine film, effectively increasing the copper ion loading of the microcapsule shell, thus generating a porous cuprous oxide structure with a large specific surface area during the subsequent copper ion reduction process. On the other hand, during application, it can attract compounds released from asphalt to the vicinity of the slow-release modified microcapsules, increasing the difficulty of these compounds volatilizing while allowing the cuprous oxide shell of the microcapsules to adsorb more harmful compounds, and causing the smoke-suppressing active components on the surface of the microcapsules to react with more of the above-mentioned compounds, thereby effectively reducing the impact of irritating gases released by asphalt during application on the human body.

[0132] (3) The composite shell material of the odor-neutralizing and temperature-controlled microcapsule of the present invention includes an inorganic base shell / barium titanate nanoparticles / polydopamine / cuprous oxide. Cuprous oxide has multiple functions. The first function is that cuprous oxide itself has extremely high adsorption capacity for sulfur-containing compounds, which can effectively reduce the malodorous sulfides generated by asphalt during application. The second function is that after being synthesized by the method described in the present invention, cuprous oxide will form a porous structure with a large specific surface area on the surface of the microcapsule, which effectively improves the adsorption capacity of cuprous oxide for harmful substances in asphalt fumes. The third function is that cuprous oxide has extremely strong catalytic activity, which can catalyze the reaction between the smoke-suppressing compounds on the surface of the odor-neutralizing and temperature-controlled microcapsule and pollutants, further improving the smoke-suppressing ability of the odor-neutralizing and temperature-controlled microcapsule.

[0133] (4) The odor-neutralizing and temperature-controlled microcapsules of the present invention can regulate the temperature of asphalt pavement in situ, which can not only effectively improve the high-temperature performance of asphalt pavement, but also reduce the damage of temperature changes to asphalt pavement and extend the service life of asphalt pavement.

[0134] (5) The odor-neutralizing and temperature-controlled microcapsules of the present invention can reduce the temperature of asphalt pavement during application after being added to asphalt. This can not only effectively reduce the urban heat island effect, but also prevent asphalt pavement from releasing various harmful substances due to excessive temperature, thereby avoiding the generation of photochemical smog and haze.

[0135] (6) The environmentally friendly asphalt described in this invention contains odor-neutralizing active components that can quickly and effectively reduce the asphalt fumes generated by the action of heat and oxygen during the production, construction and service of asphalt. It can further reduce the asphalt fumes generated during the window period when the odor-neutralizing and temperature-controlled asphalt additives are added to asphalt and the odor-neutralizing and temperature-controlled microcapsules are not effective.

[0136] (7) The odor-free and temperature-controlled asphalt mixture of the present invention can effectively improve the bonding strength between asphalt and aggregate and improve the road performance of asphalt mixture after being incorporated into the mixture as a mineral powder component. Detailed Implementation

[0137] To further illustrate the technical solution of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0138] The sulfides in the asphalt flue gas described in this invention are tested according to the standard GB_T 33318-2016 Determination of Sulfides by Gas Analysis using the sulfur chemiluminescence gas chromatography method.

[0139] The volatile organic compounds in the asphalt fumes described in this invention were tested using a Thermo Fisher Scientific TVA 2020 Toxic Volatile Gas Detector, and the test results were obtained from the FID detector in the instrument.

[0140] The asphalt fumes described in this invention were tested using the asphalt fumes enrichment and collection device described in Example 1 of Chinese Patent CN220912767U.

[0141] Example 1

[0142] a: Preparation of deodorizing and temperature-controlled microcapsules:

[0143] (1): Preparation of barium titanate nanoparticles:

[0144] S1: Weigh 18 parts by weight of tetrabutyl titanate and 12 parts by weight of butanediol and add them to a flask. Stir at 60°C and 400 rpm for 1 hour to obtain a titanium precursor solution.

[0145] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 10, and continue stirring at 400 rpm for 1 hour at 60℃ to obtain titanium precursor sol.

[0146] S3: Add 25 parts by weight of Ba(OH)2·8H2O and 25 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 85°C.

[0147] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 120℃, stir at 400 rpm for 18 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0148] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 5 parts by weight of hexadecyltrimethylammonium bromide to 50 parts by weight of formamide. Modify by stirring at 200 rpm for 5 hours at 160°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0149] (2): 5 parts by mass of n-eicosane were heated and melted at 50°C, and 50 parts by mass of N,N-dimethylformamide and 1.5 parts by mass of barium titanate nanoparticles prepared in step (1) were added. The mixture was stirred at 50°C and 500 rpm for 5 hours.

[0150] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 500 rpm for 5 hours to obtain Pickering emulsion.

[0151] (4): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (3) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 500 rpm for 4.5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours.

[0152] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 7 mg / mL. Stir at 300 rpm for 18 hours at 35°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0153] (6): 1.25 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 hour at 110°C.

[0154] (7): Add 4.5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution and stir at 300 rpm for 2 h at 55 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder and vacuum dry at -30 °C for 5 h.

[0155] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10.5 using dilute potassium hydroxide solution, and stir for 3 hours at 80°C and 300 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2.5 parts by mass of chloromethyltriisopropoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0156] (9): After stirring 9 parts by mass of the smoke-suppressing compound, jasmine aldehyde and allyl ionone in equal mass ratio, and mixing them evenly, add 1 part by mass of the solid material obtained in step (8) to 50 parts by mass of anhydrous ethanol, then add 1 part by mass of KOH, and reflux at 95°C for 7 hours. Then filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules is 3.93-9.18 μm, and the loading of the active smoke-suppressing compound accounts for 14.1 wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0157] b: Preparation of environmentally friendly asphalt:

[0158] I: Hexadecyl maleimide, pentaerythritol tetra-(dibutylhydroxyhydrogenated cinnamic acid) ester, tris(2-cyclohexylphenyl) phosphite, and p-(dipropylamino)benzaldehyde were mixed in equal proportions and dispersed in 4 parts by weight of catalytic cracking slurry. Then, 0.5 parts by weight of N-2-aminoethyl-3-aminopropylmethyldimethoxysilane and 0.5 parts by weight of octylphenol polyoxyethylene ether were added and stirred at 65°C and 450 rpm for 3 hours.

[0159] II: 3.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 250,000, 4.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 28 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 150°C for 1 hour and an extrusion temperature of 150°C to obtain asphalt additive.

[0160] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 65 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0161] c: Mix 0.5 parts by weight of the odor-free and temperature-controlled microcapsules obtained in step a, 5 parts by weight of the environmentally friendly asphalt in a molten state at 150°C obtained in step b, and 94.6 parts by weight of AC-13 graded aggregate conforming to the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement" which has been kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain the asphalt mixture.

[0162] Example 2

[0163] a: Preparation of deodorizing and temperature-controlled microcapsules:

[0164] (1): Preparation of barium titanate nanoparticles:

[0165] S1: Weigh 12 parts by weight of tetrabutyl titanate and 12 parts by weight of butanediol and add them to a flask. Stir at 55°C and 400 rpm for 3 hours to obtain a titanium precursor solution.

[0166] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 9.5, and continue stirring at 400 rpm for 3 hours at 55℃ to obtain titanium precursor sol.

[0167] S3: Add 17 parts by weight of Ba(OH)2·8H2O and 20 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 85°C.

[0168] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 120℃, stir at 400 rpm for 18 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0169] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 5 parts by weight of hexadecyltrimethylammonium bromide to 50 parts by weight of formamide. Modify by stirring at 200 rpm for 5 hours at 160°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0170] (2): 5.4 parts by mass of n-octadecane were heated and melted at 45°C, and 50 parts by mass of N,N-dimethylformamide and 1.5 parts by mass of barium titanate nanoparticles obtained in step (1) were added. The mixture was stirred at 50°C and 500 rpm for 5 hours.

[0171] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 500 rpm for 5 hours to obtain Pickering emulsion.

[0172] (4): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (3) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 500 rpm for 4.5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours.

[0173] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 9. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 10 mg / mL. Stir at 300 rpm for 18 hours at 40°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0174] (6): 1.25 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 hour at 110°C.

[0175] (7): Add 4.5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution and stir at 300 rpm for 2 h at 55 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder and vacuum dry at -30 °C for 5 h.

[0176] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10.5 using dilute potassium hydroxide solution, and stir for 3 hours at 80°C and 300 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2.5 parts by mass of chloromethyltriisopropoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0177] (9): After stirring 9 parts by mass of the smoke-suppressing compound, jasmine aldehyde and allyl ionone in equal mass ratio, and mixing them evenly, add 1 part by mass of the solid material obtained in step (8) to 50 parts by mass of anhydrous ethanol, then add 1 part by mass of KOH, and reflux at 95°C for 7 hours. Then filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules is 4.05-9.45 μm, and the loading of the active smoke-suppressing compound accounts for 14.6 wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0178] b: Preparation of environmentally friendly asphalt:

[0179] I: Hexadecyl maleimide, pentaerythritol tetra-(dibutylhydroxyhydrogenated cinnamic acid) ester, tris(2-cyclohexylphenyl) phosphite, and p-(dipropylamino)benzaldehyde were mixed in equal proportions and dispersed in 4 parts by weight of catalytic cracking slurry. Then, 0.5 parts by weight of N-2-aminoethyl-3-aminopropylmethyldimethoxysilane and 0.5 parts by weight of octylphenol polyoxyethylene ether were added and stirred at 65°C and 450 rpm for 3 hours.

[0180] II: 3.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 250,000, 4.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 28 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 150°C for 1 hour and an extrusion temperature of 150°C to obtain asphalt additive.

[0181] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 65 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0182] c: Mix 0.5 parts by weight of the odor-free and temperature-controlled microcapsules obtained in step a, 5 parts by weight of the environmentally friendly asphalt in a molten state at 150°C obtained in step b, and 94.6 parts by weight of AC-13 graded aggregate conforming to the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement" which has been kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain the asphalt mixture.

[0183] Example 3

[0184] a: Preparation of deodorizing and temperature-controlled microcapsules:

[0185] (1): Preparation of barium titanate nanoparticles:

[0186] S1: Weigh 14.5 parts by weight of tetrabutyl titanate and 12 parts by weight of ethylene glycol and add them to the flask.

[0187] A titanium precursor solution was prepared by stirring at 55℃ and 400 rpm for 1 hour.

[0188] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 10.5, and continue stirring at 400 rpm for 1 hour at 55℃ to obtain titanium precursor sol.

[0189] S3: Add 20 parts by weight of Ba(OH)2·8H2O and 20 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 85°C.

[0190] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 150℃, stir at 450 rpm for 15 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0191] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 3 parts by weight of hexadecyltrimethylammonium bromide to 30 parts by weight of dimethylphosphoramide. Modify by stirring at 200 rpm for 5 hours at 160°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0192] (2): 5 parts by mass of n-eicosane were heated and melted at 50°C, and 50 parts by mass of N,N-dimethylformamide and 1.5 parts by mass of barium titanate nanoparticles prepared in step (1) were added. The mixture was stirred at 50°C and 500 rpm for 5 hours.

[0193] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of butyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 500 rpm for 5 hours to obtain Pickering emulsion.

[0194] (4): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (3) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 500 rpm for 4.5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours.

[0195] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 7 mg / mL. Stir at 300 rpm for 18 hours at 35°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0196] (6): Mix 1.15 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 hour at 110°C.

[0197] (7): Add 4.5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution and stir at 300 rpm for 2 h at 55 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder and vacuum dry at -30 °C for 5 h.

[0198] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10.5 using dilute potassium hydroxide solution, and stir for 3 hours at 80°C and 300 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2.5 parts by mass of chloromethyltriisopropoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0199] (9): After stirring 9 parts by mass of the smoke-suppressing compound, jasmine aldehyde and allyl ionone in equal mass ratio, and mixing them evenly, add 1 part by mass of the solid material obtained in step (8) to 50 parts by mass of anhydrous ethanol, then add 1 part by mass of KOH, and reflux at 95°C for 7 hours. Then filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules is 3.88-9.05μm, and the loading of the active smoke-suppressing compound accounts for 13.1wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0200] b: Preparation of environmentally friendly asphalt:

[0201] I: Hexadecyl maleimide, pentaerythritol tetra-(dibutylhydroxyhydrogenated cinnamic acid) ester, tris(2-cyclohexylphenyl) phosphite, and p-(dipropylamino)benzaldehyde were mixed in equal proportions and dispersed in 4 parts by weight of catalytic cracking slurry. Then, 0.5 parts by weight of N-2-aminoethyl-3-aminopropylmethyldimethoxysilane and 0.5 parts by weight of octylphenol polyoxyethylene ether were added and stirred at 65°C and 450 rpm for 3 hours.

[0202] II: 3.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 250,000, 4.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 28 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 150°C for 1 hour and an extrusion temperature of 150°C to obtain asphalt additive.

[0203] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 65 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0204] c: Mix 0.5 parts by weight of the odor-free and temperature-controlled microcapsules obtained in step a, 5 parts by weight of the environmentally friendly asphalt in a molten state at 150°C obtained in step b, and 94.6 parts by weight of AC-13 graded aggregate conforming to the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement" which has been kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain the asphalt mixture.

[0205] Example 4

[0206] a: Preparation of deodorizing and temperature-controlled microcapsules:

[0207] (1): Preparation of barium titanate nanoparticles:

[0208] S1: Weigh 16 parts by weight of tetrabutyl titanate and 10 parts by weight of methanol and add them to a flask. Stir at 35°C and 400 rpm for 2 hours to obtain a titanium precursor solution.

[0209] S2: Slowly add 10wt% ammonia water to the S1 solution until the pH of the reaction system is 10.5, and continue stirring at 400 rpm for 2 hours at 35℃ to obtain titanium precursor sol.

[0210] S3: Add 22.3 parts by weight of Ba(OH)2·8H2O and 23 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 85°C.

[0211] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 140℃, stir at 400 rpm for 16 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0212] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 8 parts by weight of octadecyltrimethylammonium chloride to 30 parts by weight of formamide. Modify by stirring at 200 rpm for 5 hours at 160°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0213] (2): 5 parts by mass of n-eicosane were heated and melted at 50°C, and 50 parts by mass of N,N-dimethylformamide and 1.5 parts by mass of barium titanate nanoparticles prepared in step (1) were added. The mixture was stirred at 50°C and 500 rpm for 5 hours.

[0214] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 500 rpm for 5 hours to obtain Pickering emulsion.

[0215] (4): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (3) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 500 rpm for 4.5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours.

[0216] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 7 mg / mL. Stir at 300 rpm for 18 hours at 35°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0217] (6): 1.25 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 hour at 110°C.

[0218] (7): Add 4.5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution and stir at 300 rpm for 2 h at 55 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder and vacuum dry at -30 °C for 5 h.

[0219] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10.5 using dilute potassium hydroxide solution, and stir for 3 hours at 80°C and 300 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2.5 parts by mass of chloromethyltriisopropoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0220] (9): After stirring 9 parts by mass of the smoke-suppressing compound, jasmine aldehyde and allyl ionone in equal mass ratio, and mixing them evenly, add 1 part by mass of the solid material obtained in step (8) to 50 parts by mass of anhydrous ethanol, then add 1 part by mass of KOH, and reflux at 95°C for 7 hours. Then filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules is 3.93-9.18 μm, and the loading of the active smoke-suppressing compound accounts for 14.1 wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0221] b: Preparation of environmentally friendly asphalt:

[0222] I: Mix 3 parts by weight of 1-(2-methylphenyl)-1H-pyrrole-2,5-dione, tert-butylhydroquinone, tris(nonylphenol) phosphite, and N,N-diethyl-p-aminobenzaldehyde in equal proportions, disperse them in 4 parts by weight of extracted oil, and further add 0.5 parts by weight of 3-aminopropyltriethoxysilane and 0.5 parts by weight of dinonylphenol polyoxyethylene ether. Stir and mix at 70°C and 450 rpm for 3 hours.

[0223] II: 3.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 250,000, 4.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 28 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 150°C for 1 hour and an extrusion temperature of 150°C to obtain asphalt additive.

[0224] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 65 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0225] c: Mix 0.5 parts by weight of the odor-free and temperature-controlled microcapsules obtained in step a, 5 parts by weight of the environmentally friendly asphalt in a molten state at 150°C obtained in step b, and 94.6 parts by weight of AC-13 graded aggregate conforming to the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement" which has been kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain the asphalt mixture.

[0226] Example 5

[0227] a: Preparation of deodorizing and temperature-controlled microcapsules:

[0228] (1): Preparation of barium titanate nanoparticles:

[0229] S1: Weigh 10 parts by weight of tetrabutyl titanate and 6 parts by weight of butanediol and add them to a flask. Stir at 60°C and 400 rpm for 1.5 h to obtain a titanium precursor solution.

[0230] S2: Slowly add 10wt% ammonia water to the S1 solution until the pH of the reaction system is 10.5, and continue stirring at 400 rpm for 2 hours at 60℃ to obtain titanium precursor sol.

[0231] S3: Add 14 parts by weight of Ba(OH)2·8H2O and 16 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 90°C.

[0232] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 120℃, stir at 400 rpm for 18 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0233] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 5 parts by weight of hexadecyltrimethylammonium bromide to 50 parts by weight of formamide. Modify by stirring at 200 rpm for 5 hours at 160°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0234] (2): 5 parts by mass of n-eicosane were heated and melted at 50°C, and 50 parts by mass of N,N-dimethylformamide and 1.5 parts by mass of barium titanate nanoparticles prepared in step (1) were added. The mixture was stirred at 50°C and 500 rpm for 5 hours.

[0235] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 500 rpm for 5 hours to obtain Pickering emulsion.

[0236] (4): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (3) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 500 rpm for 4.5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours.

[0237] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 7 mg / mL. Stir at 300 rpm for 18 hours at 35°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0238] (6): Mix 1.2 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 hour at 110°C.

[0239] (7): Add 4.5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution and stir at 300 rpm for 2 h at 55 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder and vacuum dry at -30 °C for 5 h.

[0240] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10.5 using dilute potassium hydroxide solution, and stir for 3 hours at 80°C and 300 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2.5 parts by mass of chloromethyltriisopropoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0241] (9): After stirring 7 parts by mass of the equal mass ratio of the smoke-suppressing compounds: citronellal and menthone evenly, add 1 part by mass of the solid material obtained in step (8) to 50 parts by mass of anhydrous ethanol, then add 1 part by mass of KOH, and reflux at 95°C for 7 hours. Then filter and wash the bottom solid powder, and vacuum dry at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules is 3.89-9.07μm, and the loading of the active smoke-suppressing compounds accounts for 12.8wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0242] b: Preparation of environmentally friendly asphalt:

[0243] I: 3 parts by weight of 4-maleimide phenol, pentaerythritol tetrakis-(dibutylhydroxyhydrogenated cinnamic acid) ester, tris(2-cyclohexylphenyl) phosphite, and 4-(diethylamino)salicylaldehyde were mixed in equal proportions and dispersed in 4 parts by weight of catalytic cracking slurry. 0.5 parts by weight of N-2-aminoethyl-3-aminopropylmethyldimethoxysilane and 0.5 parts by weight of octylphenol polyoxyethylene ether were then added and stirred at 450 rpm for 3 hours at 65°C.

[0244] II: 3.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 250,000, 4.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 28 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 150°C for 1 hour and an extrusion temperature of 150°C to obtain asphalt additive.

[0245] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 65 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0246] c: Mix 0.35 parts by weight of the odor-free and temperature-controlled microcapsules obtained in step a, 5 parts by weight of the environmentally friendly asphalt in a molten state at 150°C obtained in step b, and 94.6 parts by weight of AC-13 graded aggregate conforming to the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement" which has been kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain the asphalt mixture.

[0247] Comparative Example 1

[0248] Five parts by weight of base asphalt (65 1 / 10 mm penetration at 25℃) and 95 parts by weight of AC-13 graded aggregate conforming to the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement" were mixed and stirred at 148℃ for 1.5 minutes to obtain asphalt mixture.

[0249] Comparative Example 2

[0250] a: Preparation of environmentally friendly asphalt:

[0251] I: Hexadecyl maleimide, pentaerythritol tetra-(dibutylhydroxyhydrogenated cinnamic acid) ester, tris(2-cyclohexylphenyl) phosphite, and p-(dipropylamino)benzaldehyde were mixed in equal proportions and dispersed in 4 parts by weight of catalytic cracking slurry. Then, 0.5 parts by weight of N-2-aminoethyl-3-aminopropylmethyldimethoxysilane and 0.5 parts by weight of octylphenol polyoxyethylene ether were added and stirred at 65°C and 450 rpm for 3 hours.

[0252] II: 3.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 250,000, 4.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 28 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 150°C for 1 hour and an extrusion temperature of 150°C to obtain asphalt additive.

[0253] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 65 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0254] b: Mix 5 parts by weight of the environmentally friendly asphalt obtained in step b at 150°C in a molten state with 95 parts by weight of AC-13 graded aggregate that meets the requirements of the Ministry of Transport's "JTG F40-2004 Technical Specification for Construction of Highway Asphalt Pavement" and keep it at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain asphalt mixture.

[0255] Test Example 1

[0256] Sulfides and volatile organic compounds are harmful substances that are generated during the construction of asphalt pavement and asphalt mixtures, which have a significant impact on human health. The asphalt mixture samples prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to flue gas enrichment at a temperature of 153°C for 8 hours. The data obtained are shown in Table 1.

[0257] Table 1

[0258] Test sample Sulfide content, ppm Volatile organic compound content, ppm Example 1 134.50 366.39 Example 2 139.88 392.57 Example 3 172.16 471.08 Example 4 150.64 388.64 Example 5 195.44 498.19 Comparative Example 1 537.99 1308.55 Comparative Example 2 344.31 889.81 Comparative Example 3 425.01 1056.00

[0259] Test Example 2

[0260] To investigate the emission of flue gas from the asphalt samples during service, the asphalt samples prepared in Examples 1-5 and Comparative Examples 1-2 were further fabricated into Marshall specimens with the following dimensions: Flue gas enrichment was carried out at a temperature of 70℃ for 36 hours. After enrichment, the gas in the sealed container was sampled and tested. The data obtained are shown in Table 2.

[0261] Table 2

[0262]

[0263]

[0264] Test Example 3

[0265] The anti-stripping performance of asphalt mixtures was evaluated using the Los Angeles abrasion tester produced by Beijing High-speed Railway Construction Technology Development Co., Ltd., and the test method specified in "T0733—2011 Kentaburg Asphalt Mixture Stripping Test" of the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" of the Ministry of Transport. The data obtained are shown in Table 3.

[0266] Table 3

[0267] Test sample Mixture loss rate, % Example 1 5.30 Example 2 5.72 Example 3 6.86 Example 4 5.50 Example 5 6.81 Comparative Example 1 27.90 Comparative Example 2 18.69

[0268] The specific embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An asphalt mixture, characterized in that, The asphalt mixture, by weight, comprises the following components: Graded stone: 92.5-95.8 parts per unit area; Environmentally friendly asphalt: 4-6 parts; Odor-neutralizing and temperature-controlled microcapsules: 0.2-1.5 parts, preferably 0.4-1.0 parts; The odor-neutralizing and temperature-controlled microcapsule comprises a composite shell and a core material. The composite shell comprises an inorganic base shell, barium titanate nanoparticles, polydopamine, and cuprous oxide. The core material comprises n-alkanes with a phase transition temperature of 40-60°C. The surface of the composite shell is loaded with an active smoke-suppressing compound.

2. The asphalt mixture according to claim 1, characterized in that, The environmentally friendly asphalt, by weight, comprises the following components: Odor-neutralizing active ingredient: 0.05-10 parts; Dispersant: 1-20 parts; Silane coupling agent: 0.1-10 parts; Ether compounds: 0.1-10 parts; Styrene-butadiene-styrene polymer: 1-20 parts; Ethylene-vinyl acetate copolymer: 1-20 parts; Base bitumen: 50-500 parts.

3. The asphalt mixture according to claim 2, characterized in that, The deodorizing active ingredient is selected from one or more of the following: imide compounds with more than 9 carbon atoms, antioxidants with more than 14 carbon atoms, and aromatic amino compounds with more than 10 carbon atoms. And / or, the dispersant is one or more of the following: extracted oil, furfural refined oil, and catalytic cracking slurry oil; And / or, the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane; And / or, the ether compound is selected from polyoxyethylene ether compounds containing at least one benzene ring in the molecular chain, preferably selected from one or more of octylphenol polyoxyethylene ether, dinonylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and dodecylphenol polyoxyethylene ether. And / or, the styrene-butadiene-styrene copolymer is linear and / or star-shaped, with an average relative molecular mass of 100,000 to 300,000; And / or, in the ethylene-vinyl acetate copolymer, the mass content of vinyl acetate is 20wt% to 30wt% based on the mass of the ethylene-vinyl acetate copolymer; And / or, the 25°C penetration of the base bitumen is 30-210 1 / 10 mm.

4. The asphalt mixture according to claim 2, characterized in that, The particle size of the odor-neutralizing and temperature-controlled microcapsules is 1-12 μm; And / or, the mass ratio of the composite shell material to the core material of the odor-neutralizing and temperature-controlled microcapsule is 1:(0.2-2); And / or, the composite shell material comprises an inorganic base shell / barium titanate nanoparticles / polydopamine / cuprous oxide, wherein the mass ratio of the inorganic base shell to the barium titanate nanoparticles is 1:(0.2-0.8), the mass ratio of the inorganic base shell to the polydopamine is 1:(0.1-0.5), and the mass ratio of the inorganic base shell to the cuprous oxide is 1:(0.5-2); And / or, the material of the inorganic base shell is selected from at least one of silicon dioxide and titanium dioxide, preferably silicon dioxide; And / or, the n-alkane with a phase transition temperature of 40-60°C is one or more of n-octadecane, n-eicosane, and n-docosahexadecane; And / or, the loading of the active smoke-suppressing compound accounts for 0.1wt%-20wt% of the total mass of the odor-neutralizing and temperature-controlled microcapsules; And / or, the active smoke-suppressing compound is selected from one or more aldehyde compounds with a molecular weight greater than 160 and ketone compounds with a molecular weight greater than 150.

5. A method for preparing the asphalt mixture according to any one of claims 1-4, comprising: a: Preparation of flavor-neutralizing and temperature-controlled microcapsules; b: Prepare environmentally friendly asphalt; c: Heat the environmentally friendly asphalt obtained in step b to a molten state, mix it with the odor-free and temperature-controlled microcapsules and graded aggregates obtained in step a, and stir to obtain asphalt mixture.

6. The method according to claim 5, characterized in that, Step a, the method for preparing odor-neutralizing and temperature-controlled microcapsules, includes: (1) Preparation of barium titanate nanoparticles; (2) Heat the core material raw material to melt, and mix it with solvent and barium titanate nanoparticles obtained in step (1); (3) Add the inorganic base shell precursor to the reaction system of step (2), stir and mix to obtain Pickering emulsion; (4) Adjust the pH value of the Pickering emulsion, continue stirring, then age, filter, wash, and freeze dry; (5) Add the solid material obtained in step (4) to the buffer solution, add dopamine hydrochloride, stir and process, then filter, wash and freeze dry; (6) Add the solid particles and copper ion solution obtained in step (5) into the reaction vessel and carry out the reaction with stirring; (7) Mix the reducing agent with the buffer solution, stir to dissolve, and then add it to the reaction system of step (6). Stir to carry out the reaction, then filter, wash, and freeze dry. (8) Mix the solid particles obtained in step (7) with water, adjust the pH, and then heat and stir; then add silane coupling agent, continue to react under stirring, and then filter, wash and freeze dry. (9) The solid material obtained in step (8), the active smoke-suppressing compound, and the strong alkali are added to an organic solvent to react. After cooling, filtering, washing, and freeze-drying, the odor-neutralizing temperature-controlled microcapsules are obtained.

7. The method according to claim 6, characterized in that, Step (1) of preparing barium titanate nanoparticles includes: S1: Stir and mix the titanium precursor and solvent; S2: Adjust the pH of the mixed solution obtained in S1 and stir until a titanium precursor sol is obtained; S3: Mix the barium precursor with water; S4: The titanium precursor sol obtained in S2 is mixed with the mixture obtained in S3 and reacted under stirring. After the reaction is completed, the mixture is filtered, washed, freeze-dried, and ground to obtain primary barium titanate nanoparticles. S5: Primary barium titanate nanoparticles, surfactants and solvents are mixed and modified under stirring. After modification, the mixture is washed and freeze-dried to obtain barium titanate nanoparticles.

8. The method according to claim 7, characterized in that, In step S1, the titanium precursor is selected from at least one of tetraethyl titanate, n-propyl titanate, and tetrabutyl titanate. And / or, in step S1, the solvent is an alcohol compound with a boiling point >60°C, and the alcohol compound is an anhydrous alcohol compound, preferably at least one of methanol, butanediol, ethylene glycol, n-butanol, and ethanol; And / or, in step S1, the stirring temperature is 25-60℃; the stirring speed is 200-500 rpm; and the stirring time is 0.5-3 hours. And / or, in step S1, the mass ratio of the titanium precursor to the solvent is (1-20):

1.

9. The method according to claim 7, characterized in that, In step S2, the pH of the S1 mixed solution is adjusted to pH = 9-12; And / or, in step S2, the stirring temperature is 25-60℃; the stirring speed is 200-500 rpm; and the stirring time is 0.5-3 hours.

10. The method according to claim 7, characterized in that, In step S3, the barium precursor is at least one of Ba(OH)2, Ba(OH)2·H2O, and Ba(OH)2·8H2O. And / or, in step S3, the stirring temperature is 80-120℃; the stirring speed is 200-500 rpm; and the stirring time is 2-5 hours.

11. The method according to claim 7, characterized in that, In step S4, the molar ratio of the mixture obtained in S3 (based on barium) to the titanium precursor sol obtained in S2 (based on titanium) is 1:(0.5-5). And / or, the stirring speed is 200-500 rpm; the reaction temperature is 100-200℃; and the reaction time is 2-48 hours. And / or, in step S4, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

12. The method according to claim 7, characterized in that, In step S5, the diameter of the barium titanate nanoparticles is 20-100 nm; And / or, in step S5, the surfactant is an anionic surfactant, preferably at least one of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and 2-morpholine ethanesulfonic acid; And / or, in step S5, the solvent is an aprotic solvent with a boiling point >100℃, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide; And / or, in step S5, the stirring speed is 200-500 rpm; The modification temperature is 70-180℃, and the modification time is 2-8 hours; And / or, in step S5, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

13. The method according to claim 6, characterized in that, In step (2), the solvent is an aprotic solvent with a boiling point >100℃, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide; And / or, in step (2), the mass ratio of the solvent to the barium titanate nanoparticles is (20-80):1; And / or, in step (2), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

14. The method according to claim 6, characterized in that, In step (3), the inorganic base shell precursor is at least one of silicate ester compounds and titanate ester compounds, preferably a silicate ester compound; the silicate ester compound is preferably at least one of methyl silicate, tetraethyl orthosilicate, tetraethyl orthosilicate, and tetrabutyl orthosilicate. And / or, in step (3), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

15. The method according to claim 6, characterized in that, In step (4), adjust the pH value to 3-6; And / or, in step (4), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours; And / or, in step (4), the aging conditions are: standing at 40-80°C for 12-30 hours.

16. The method according to claim 6, characterized in that, In step (5), the buffer solution is one or more of phosphate buffer, carbonate buffer, and tris(hydroxymethyl)aminomethane hydrochloride buffer; And / or, in step (5), the pH value of the buffer solution is 8-10; And / or, in step (5), the mass ratio of the buffer solution to the solid material obtained in step (4) is (10-100):1; And / or, in step (5), after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL; And / or, in step (5), the stirring speed is 100-300 rpm, the stirring temperature is 20-40℃, and the stirring time is 12-24 hours.

17. The method according to claim 6, characterized in that, In step (6), the copper ion solution has a copper ion concentration of 0.05-0.5 mol / L; And / or, in step (6), the mass ratio of the solid particles obtained in step (5) to the copper ion solution is 1:(50-200); And / or, in step (6), the stirring speed is 100-450 rpm, the reaction temperature is 100-190°C, and the reaction time is 1-5 hours.

18. The method according to claim 6, characterized in that, In step (7), the reducing agent is a sulfite reducing agent, preferably selected from at least one of potassium sulfite and sodium sulfite; the pH value of the buffer solution is 4.5-6.5; And / or, in step (7), the mass ratio of the reducing agent to the buffer solution is 1:(10-20); And / or, in step (7), when stirring to dissolve, the stirring speed is 200-450 rpm, the stirring temperature is 40-80℃, and the stirring time is 1-5 hours; And / or, in step (7), the stirring speed is 100-450 rpm, the reaction temperature is 60-95°C, and the reaction time is 2-5 hours.

19. The method according to claim 6, characterized in that, In step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-6h; And / or, in step (8), adjust the pH to 9-11; And / or, in step (8), the mass ratio of the solid particles obtained in step (7) to water is 1:(10-50); And / or, in step (8), the added silane coupling agent is selected from one or more of chloropropyltriethoxysilane, chloromethyltriethoxysilane, dichloromethyltriethoxysilane, and chloromethyltriisopropoxysilane; And / or, in step (8), the mass ratio of the solid particles obtained in step (7) to the silane coupling agent is 1:(0.5-4); And / or, in step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-8h.

20. The method according to claim 6, characterized in that, In step (9), the organic solvent is selected from one or more of methanol, butanediol, ethylene glycol, n-butanol, and anhydrous ethanol; And / or, in step (9), the mass ratio of the solid material obtained in step (8) to the organic solvent is 1:(20-80); the mass ratio of the solid material obtained in step (8) to the strong alkali is 1:(0.5-2); And / or, in step (9), the reaction conditions are: a reaction temperature of 80-210℃ and a reaction time of 5-10 hours.

21. The method according to claim 5, characterized in that, Step (b) is a method for preparing environmentally friendly asphalt, including: I: Heat and stir to mix the odor-neutralizing active ingredient, silane coupling agent, dispersant, and ether compound; II: The styrene-butadiene-styrene polymer, ethylene-vinyl acetate copolymer and the mixture obtained in step I are mixed and extruded to obtain asphalt additive; III: The asphalt additive obtained in step II is mixed with the molten base asphalt to obtain environmentally friendly asphalt.

22. The method according to claim 5, characterized in that, In step c, the environmentally friendly asphalt is heated to a melting temperature of 133℃-163℃; And / or, in step c, the graded stone is subjected to heat preservation treatment before use, the heat preservation temperature is 160-190℃, and the heat preservation time is 3-5h; And / or, in step c, the mixing conditions are: mixing temperature of 133-163℃ and mixing time of 0.5min-3min.

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