An asphalt mixture and a method for producing the same

Abstract

The present application provides a kind of asphalt mixture and its preparation method.The asphalt mixture of the present application includes the following components by weight parts: graded stone: 93-95.9 parts;Environmental friendly microcapsule group: 0.1-1 part;Environmental friendly asphalt: 4-6 parts;The environmental friendly microcapsule group includes first microcapsule, second microcapsule and third microcapsule, wherein the first microcapsule, the second microcapsule and the third microcapsule each include capsule core and capsule wall, the capsule core is wrapped in the capsule wall, the capsule core contains active component, the capsule wall includes inner wall layer and outer wall layer, the inner wall layer is barium titanate resin composite wall, and the outer wall layer is rubber material.The asphalt mixture of the present application not only significantly reduces the amount of asphalt smoke released during application compared to ordinary asphalt mixture, but also has strong anti-stripping ability.

Description

Technical Field

[0001] This invention belongs to the field of road asphalt technology, specifically relating to an environmentally friendly anti-stripping asphalt mixture and its preparation method. Background Technology

[0002] Asphalt mixtures release large amounts of toxic and harmful substances such as sulfides and volatile organic compounds during production, construction, and service, which pollute the ecological environment and threaten human health.

[0003] Researchers have attempted to reduce asphalt fume emissions by adding reactive substances to asphalt. For example, CN118702965A discloses a odor-neutralizing asphalt functional improver, its preparation method, and its application. However, the chemicals introduced by this method are prone to denaturation and volatilization under high-temperature conditions, which can affect the smoke-suppressing effect in practical applications. Other researchers have incorporated smoke suppressants and other substances into asphalt to reduce the amount of asphalt fume generated and mitigate health hazards to construction workers. These substances include graphene, activated carbon, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, copper hydroxide, and iron hydroxide, as specifically described in additives such as those in CN202311170186.0 and CN202310163261.4. However, these additives exhibit poor compatibility with asphalt mixtures, significantly affecting the adhesion strength between asphalt and aggregates, leading to quality problems such as aggregate loss in the asphalt mixture. Summary of the Invention

[0004] In view of the problems existing in the prior art, the present invention provides an asphalt mixture and its preparation method. Compared with ordinary asphalt mixtures, the asphalt mixture of the present invention not only significantly reduces the amount of asphalt fume released during application, but also has a stronger anti-stripping ability.

[0005] The first aspect of this invention provides an asphalt mixture, comprising the following components by weight:

[0006] Graded stone: 93-95.9 parts per unit area;

[0007] Environmentally friendly microcapsule group: 0.1-1 part, preferably 0.2-1 part;

[0008] Environmentally friendly asphalt: 4-6 parts;

[0009] The environmentally friendly microcapsule assembly includes a first microcapsule, a second microcapsule, and a third microcapsule. Each of the first, second, and third microcapsules includes a core and a wall. The core is encapsulated within the wall and contains an active component. The wall includes an inner wall layer and an outer wall layer. The inner wall layer is a barium titanate resin composite wall, and the outer wall layer is a rubber material.

[0010] 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".

[0011] Furthermore, the thickness of the capsule wall (the sum of the thicknesses of the inner and outer walls) of the first microcapsule is 0.6–2.2 μm; the thickness of the capsule wall (the sum of the thicknesses of the inner and outer walls) of the second microcapsule is greater than 2.2 μm and less than 3.3 μm; and the thickness of the capsule wall (the sum of the thicknesses of the inner and outer walls) of the third microcapsule is 3.3–5.2 μm.

[0012] Furthermore, in the environmentally friendly microcapsule, the mass ratio of the first microcapsule, the second microcapsule, and the third microcapsule is 1:(0.2-5):(0.2-5), preferably 1:(0.2-0.8):(0.2-0.8).

[0013] Further, in the first microcapsule, the mass ratio of the core, inner wall layer and outer wall layer is 1:(0.7-1):(0.2-0.5); in the second microcapsule, the mass ratio of the core, inner wall layer and outer wall layer is 1:(1.1-1.5):(0.4-0.7); and in the third microcapsule, the mass ratio of the core, inner wall layer and outer wall layer is 1:(1.7-2):(0.5-1).

[0014] Furthermore, the size of each of the first microcapsule, the second microcapsule, and the third microcapsule is independently less than 50 μm, preferably less than 20 μm, and more preferably 3-15 μm.

[0015] Furthermore, in the barium titanate resin composite wall, the mass ratio of resin to barium titanate is (0.1-8):1.

[0016] Furthermore, the barium titanate is composed of nanoparticles with a particle size of 20-100 nm.

[0017] Furthermore, the resin is at least one of melamine resin, urea-formaldehyde resin, and polymethyl methacrylate, preferably melamine resin.

[0018] Furthermore, the rubber material is at least one of chlorinated rubber, styrene-butadiene rubber, and chloroprene rubber.

[0019] Furthermore, the active component is an inhibitor for suppressing the release of asphalt fumes, preferably at least one of aldehyde compounds, alcohol compounds, phenolic compounds, and ester compounds.

[0020] Further, the aldehyde compound is selected from at least one of aliphatic aldehydes with 7 or more carbon atoms and aromatic aldehydes with 6 or more carbon atoms, more preferably from at least one of p-methylbenzaldehyde, decanal, o-carboxybenzaldehyde, p-isopropylbenzaldehyde, cinnamaldehyde, p-hydroxybenzaldehyde, p-methoxybenzaldehyde, 2-methyl-3-(3,4-methylene-dioxyphenyl)propanal, 3,4-methylenedioxybenzaldehyde, 3-(4-isopropylphenyl)-2-methylpropanal, ethyl vanillin, phenylacetaldehyde, anisaldehyde, nonadien-2,6-aldehyde, 2,6-dimethyl-2,6-octadienal, vanillin, citronellol, neraldehyde, hydroxymethylpentylcyclohexene acetal, p-diethylaminobenzaldehyde, and undecenal.

[0021] Furthermore, the ketone compound is selected from at least one of aliphatic ketones with 8 or more carbon atoms and aromatic ketones with 8 or more carbon atoms, more preferably at least one of 6-methyl-3,5-heptadien-2-one, 2-undecanone, acetophenone, ionone, irisone, methyl ionone, damasone, and dihydrodamasone.

[0022] Further, the alcohol compound is an alcohol with more than 6 carbon atoms, more preferably at least one selected from cinnamyl alcohol, menthol, cis-3,7-dimethyl-2,6-octadienol, citronellol, geraniol, myrceneol, 2,6,10-trimethyl-2,6,10-dodecanetrien-12-ol, lavenderol, benzyl alcohol, 2-phenylethanol, dihydromyrceneol, tetrahydrogeraniol, and nerolidol.

[0023] Further, the ester compound is an ester with more than 7 carbon atoms, more preferably at least one of methyl salicylate, methyl cinnamate, ethyl cinnamate, ethyl phenylacetate, methyl phenylacetate, geraniol phenylacetate, phenylethyl phenylacetate, isoamyl phenylacetate, benzyl salicylate, p-methyl benzyl acetate, benzyl acetate, isobutyl benzoate, isoamyl salicylate, benzyl cinnamate, phenylethyl cinnamate, linaloyl formate, linaloyl acetate, linaloyl isobutyrate, menthyl acetate, terpineol acetate, and borneol acetate.

[0024] Further, preferably, the active component in the first microcapsule is selected from aldehydes and / or ketones, the active component in the second microcapsule is selected from alcohols, and the active component in the third microcapsule is selected from esters.

[0025] Furthermore, the environmentally friendly asphalt, by weight, comprises the following components:

[0026] Odor-neutralizing active substance: 0.05-10 parts;

[0027] Dispersant: 1-20 parts;

[0028] Silane coupling agent: 0.1-10 parts

[0029] Styrene-butadiene-styrene polymer: 1-20 parts, preferably 4-8 parts;

[0030] Ethylene-vinyl acetate copolymer: 1-20 parts, preferably 4-8 parts;

[0031] Base bitumen: 50-500 parts.

[0032] Furthermore, the deodorizing active substance 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] Furthermore, the dispersant is one or more of the following: extracted oil, furfural refined oil, and catalytic cracking slurry.

[0037] 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.

[0038] Furthermore, the styrene-butadiene-styrene copolymer is linear and / or star-shaped, with an average relative molecular mass of 100,000 to 300,000.

[0039] 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.

[0040] Furthermore, the penetration of the base asphalt at 25°C is 30-210 1 / 10 mm. A second aspect of the present invention provides a method for preparing the above-mentioned asphalt mixture, comprising:

[0041] a: Preparation of environmentally friendly microcapsule assemblies;

[0042] b: Prepare environmentally friendly asphalt and heat it to melt;

[0043] c: Mix the environmentally friendly microcapsule group obtained in step a, the environmentally friendly asphalt in the molten state in step b, and the graded stone materials to obtain an asphalt mixture.

[0044] Furthermore, the method for preparing the environmentally friendly microcapsule assembly in step a includes:

[0045] The first microcapsule, the second microcapsule, and the third microcapsule were mixed evenly to obtain an environmentally friendly microcapsule assembly.

[0046] Furthermore, the preparation methods of the first microcapsule, the second microcapsule, and the third microcapsule each independently include:

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

[0048] (2) The active components, barium titanate nanoparticles and water are mixed to form a Pickering emulsion;

[0049] (3) The Pickering emulsion is reacted with the resin prepolymer, and then filtered, washed and freeze-dried to obtain the pre-coated material;

[0050] (4) Mix the rubber material, solvent and the pre-coated material, then mix the resulting mixture with water, stir and heat to obtain microcapsules.

[0051] Furthermore, the method for preparing barium titanate nanoparticles in step (1) includes:

[0052] S1: Stir and mix the titanium precursor and solvent;

[0053] S2: Adjust the pH of the mixed solution obtained in S1 and stir until a titanium precursor sol is obtained;

[0054] S3: Mix the barium precursor with water;

[0055] 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.

[0056] 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.

[0057] Further, in step S1, the titanium precursor is selected from at least one of tetraethyl titanate, n-propyl titanate, and tetrabutyl titanate, and is more preferably tetraethyl titanate.

[0058] 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, and more preferably anhydrous ethanol.

[0059] 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.

[0060] Further, in step S1, the mass ratio of the titanium precursor to the solvent is (1-20):1.

[0061] Further, in step S2, the pH of the S1 mixed solution is adjusted to pH = 9-12.

[0062] 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.

[0063] 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.

[0064] Further, in step S3, the barium precursor is at least one of Ba(OH)2, Ba(OH)2·H2O, and Ba(OH)2·8H2O.

[0065] Further, in step S3, the barium precursor and water are added to the reaction vessel and stirred. Further, in step S3, the water is deionized water. The mass ratio of the barium precursor to deionized water is (0.5-4):1.

[0066] 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.

[0067] 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).

[0068] 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.

[0069] Furthermore, in step S4, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0070] Furthermore, in step S4, the grinding specifically means grinding until there are no obvious lumps.

[0071] Furthermore, in step S5, the diameter of the barium titanate nanoparticles is 20-100 nm.

[0072] Further, in step S5, the surfactant is an anionic surfactant, preferably at least one of sodium dodecylbenzenesulfonate (SDBS), sodium dodecyl sulfate (SDS), and 2-morpholine ethanesulfonic acid, and more preferably sodium dodecylbenzenesulfonate.

[0073] 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.

[0074] 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.

[0075] Furthermore, in step S5, the stirring speed is 200-500 rpm; the modification temperature is 70-180℃; and the modification time is 2-58 hours.

[0076] Furthermore, in step S5, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0077] Further, in step (2), the mass ratio of the active component, barium titanate nanoparticles and water is 1:(0.1-0.8):(5-20).

[0078] Further, in step (2), the mixing is carried out under stirring, with a stirring speed of 200-500 rpm, a stirring time of 2-5 hours, and a temperature of 35-65℃.

[0079] Further, in step (3), before the Pickering emulsion reacts with the resin prepolymer, the pH value of the Pickering emulsion is adjusted to below 5, preferably 2-4. The reagent used to adjust the pH value can be a conventional inorganic acid solution, such as dilute hydrochloric acid.

[0080] Furthermore, in step (3), the reaction between the Pickering emulsion and the resin prepolymer is carried out under stirring. The stirring speed can be 400-800 rpm, the reaction temperature can be 60-90℃, and the time can be 1-5 hours.

[0081] Further, in step (3), the resin prepolymer can be one or more of melamine resin prepolymer, urea-formaldehyde resin prepolymer, and polymethyl methacrylate prepolymer. Preferably, the resin prepolymer is a melamine resin prepolymer.

[0082] Further, in step (3), the preparation method of the melamine resin prepolymer includes: mixing and dissolving melamine and formaldehyde solution with water, adjusting the pH value to 7.5-9.5, and then placing it in a constant temperature water bath at 60-90℃ and stirring at a speed of 400-800 rpm for 0.5-3.5 hours.

[0083] Furthermore, the concentration of the formaldehyde solution is 30-40 wt%.

[0084] Furthermore, the mass ratio of the melamine, the formaldehyde solution, and the water is 1:(2-3):(5-10).

[0085] Furthermore, in step (3), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0086] Further, in step (4), the mass ratio of the rubber material, the volatile solvent and water is 1:(10-200):(10-300).

[0087] Further, in step (4), the volatile solvent is a volatile solvent selected from at least one of carbon tetrachloride, dichloromethane and trichloroethylene.

[0088] Further, in step (4), the stirring speed is 200-800 rpm. The temperature is raised until the solvent evaporates.

[0089] Furthermore, step b, the method for preparing environmentally friendly asphalt, includes:

[0090] I: Heat and stir the odor-neutralizing active ingredient, silane coupling agent, and dispersant together;

[0091] 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;

[0092] III: After mixing the asphalt additive obtained in step II with the molten base asphalt, an environmentally friendly asphalt is obtained.

[0093] 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.

[0094] 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℃.

[0095] Furthermore, in step III, the base asphalt is heated to a molten state at a temperature of 133-163°C. The stirring speed is 400-600 rpm, and environmentally friendly high-performance asphalt can be obtained after stirring for 1-4 hours.

[0096] Furthermore, in step c, the environmentally friendly asphalt is heated to a melting temperature of 133℃-163℃.

[0097] 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.

[0098] Furthermore, in step c, the mixing conditions are: mixing temperature of 133-163℃ and mixing time of 0.5min-3min.

[0099] Compared with the prior art, the present invention has the following advantages:

[0100] (1) In the environmentally friendly asphalt described in this invention, based on the role of silane coupling agent, styrene-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer and odor-neutralizing active substance can be fused together during the melting and extrusion process to obtain asphalt additive. After being added to asphalt, the 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 anti-stripping performance of asphalt mixture.

[0101] (2) In the environmentally friendly microcapsule group described in this invention, by combining three microcapsules with different slow-release rates, different active components can be released at different slow-release rates, thus extending the action time of the active components. Using this asphalt additive in asphalt compositions results in longer storage and service life for the asphalt compositions. During construction, it can effectively reduce the emission of asphalt fumes and reduce environmental pollution.

[0102] (3) In the environmentally friendly microcapsule assembly described in this invention, the active component in the core of the microcapsule is selected as an inhibitor to suppress the release of asphalt fumes, and the capsule wall includes an inner wall layer and an outer wall layer. The inner wall layer is a barium titanate resin composite wall, and the outer wall layer is a rubber material. As the inner wall layer, the modified barium titanate nanoparticles, due to their nano-size, can stably exist between the water and oil interfaces during the microcapsule synthesis process. Furthermore, they can serve as template agents for microcapsule synthesis, maintaining the stability of the core material mixed droplets. On the other hand, the barium titanate nanoparticles are affected by high temperature, causing the crystal axis to distort, and thus spontaneously polarize without any external electric field, generating permanent electrodes. This attracts compounds released from asphalt under high temperature to the vibrating area around the slow-release modified microcapsules, increasing the difficulty of these compounds volatilizing, thereby effectively reducing the impact of irritating gases released from asphalt pavement on the human body.

[0103] (4) In the environmentally friendly microcapsule assembly described in this invention, the rubber material of the outer wall layer is wrapped around the inner wall layer in the form of a uniform and dense membrane material, so that the microcapsule as a whole can not only have a certain strength, but also effectively integrate with asphalt and have good compatibility.

[0104] (5) The environmentally friendly asphalt described in this invention contains odor-neutralizing active substances, which can quickly and effectively reduce the asphalt fumes generated by the action of heat and oxygen during the production, construction and service of asphalt, and can play an odor-neutralizing role during the window period when the environmentally friendly microcapsules are ineffective.

[0105] (6) The environmentally friendly anti-stripping asphalt mixture of the present invention contains environmentally friendly microcapsule groups with small size and porous surface. When added to the mixture as a mineral powder component, it can effectively improve the bonding strength between asphalt and aggregate, and further improve the anti-stripping ability of the asphalt mixture. Detailed Implementation

[0106] To further illustrate the technical solution of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0107] The hydrogen sulfide and volatile organic compounds in the asphalt fumes described in this invention were tested using a PGM-6228 gas detector.

[0108] 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.

[0109] Example 1

[0110] a: Preparation of environmentally friendly microcapsule assemblies:

[0111] (1) Preparation of barium titanate nanoparticles:

[0112] S1: Weigh 15 parts by weight of tetraethyl titanate and 10 parts by weight of anhydrous ethanol and add them to a flask. Stir for 2 hours at 60°C and 400 rpm to obtain a titanium precursor solution.

[0113] 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.

[0114] S3: Add 21 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 3 hours at 80°C.

[0115] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 160℃, stir at 400 rpm for 35 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.

[0116] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by weight of sodium dodecylbenzenesulfonate to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 4 hours at 140°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 50-80 nm).

[0117] (2) Add 1.3 parts by weight of anisaldehyde to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A1.

[0118] Add 1.3 parts by weight of cinnamyl alcohol to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A2.

[0119] Add 1.3 parts by weight of linaloyl isobutyrate to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A3.

[0120] (3) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 7 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 65℃ and stir at 800 r / min for 0.5 h to obtain melamine resin prepolymer.

[0121] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A1 to adjust the pH value to 2. 0.25 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75 °C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30 °C for 5 h to obtain the pre-coated material Y-A1.

[0122] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A2 to adjust the pH value to 2. 0.55 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A2.

[0123] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A3 to adjust the pH value to 2. 0.95 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A3.

[0124] (4) Dissolve 0.032 parts by weight of chlorinated rubber in 1 part by weight of dichloromethane, add 1 part by weight of the pre-coated material Y-A1, and mix thoroughly. Add the resulting mixture to 5 parts by weight of water, stir at 500 r / min, and raise the temperature until the solvent evaporates to obtain microcapsules W-A1. The size is 3.0-4.8 μm, the mass ratio of the core, inner wall layer and outer wall layer is 1:0.75:0.22, and the capsule wall thickness is 1.1 μm.

[0125] 0.058 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coating material Y-A2 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A2. The size of the microcapsules was 4.8-6.2 μm, the mass ratio of the core, inner wall layer and outer wall layer was 1:1.15:0.42, and the capsule wall thickness was 2.4 μm.

[0126] 0.089 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coated material Y-A3 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A3. The size of the microcapsules was 6.2-8.4 μm, the mass ratio of the core, inner wall layer and outer wall layer was 1:1.71:0.65, and the capsule wall thickness was 3.7 μm.

[0127] 0.3 parts by weight of microcapsule W-A1, 0.2 parts by weight of microcapsule W-A2, and 0.15 parts by weight of microcapsule W-A3 were mixed evenly to obtain an environmentally friendly microcapsule group.

[0128] b: Preparation of environmentally friendly asphalt:

[0129] I: Mix N-phenylmaleimide, 2,6-di-tert-butyl-p-methylphenol, tris(nonylphenol) phosphite, and 4-diethylaminobenzaldehyde in equal proportions, disperse them in 6 parts by weight of extracted oil, and further add 0.5 parts by weight of 3-aminopropyltriethoxysilane. Stir and mix at 50°C and 400 rpm for 2 hours.

[0130] II: Four parts by weight of styrene-butadiene-styrene copolymer with a relative molecular mass of 150,000, four parts by weight of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 25 wt%, and the mixture obtained in step I were kneaded in a preheated kneader at a kneading temperature of 130°C for 2 hours.

[0131] The asphalt additive was obtained by extruding at a temperature of 130℃.

[0132] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (74 1 / 10 mm penetration at 25°C) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0133] c: Mix 0.2 parts by weight of the environmentally friendly microcapsule group obtained in step a, 5 parts by weight of the environmentally friendly asphalt in the molten state at 150°C obtained in step b, and 94.8 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" after being kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain asphalt mixture.

[0134] Example 2

[0135] a: Preparation of environmentally friendly microcapsule assemblies:

[0136] (1) Preparation of barium titanate nanoparticles:

[0137] S1: Weigh 8 parts by weight of tetraethyl titanate and 8 parts by weight of n-butanol and add them to a flask. Stir for 2 hours at 60°C and 400 rpm to obtain a titanium precursor solution.

[0138] 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 2 hours at 60℃ to obtain the titanium precursor sol.

[0139] S3: Add 11 parts by weight of Ba(OH)2·8H2O and 11 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 3 hours at 80°C.

[0140] 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 38 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.

[0141] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 5 parts by weight of sodium dodecylbenzenesulfonate to 50 parts by weight of dimethylphosphoramide. Modify by stirring at 200 rpm for 8 hours at 140°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 50-80 nm).

[0142] (2) Add 1.2 parts by weight of methyl ionone to 8.1 parts by weight of water at 55°C, add 0.7 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A1.

[0143] Add 1.2 parts by weight of lavender alcohol to 8.1 parts by weight of water at 55°C, add 0.7 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A2.

[0144] 1.2 parts by weight of geraniol phenylacetate were added to 8.1 parts by weight of water at 55°C, and 0.7 parts by weight of modified barium titanate nanoparticles were added. The mixture was stirred at 400 r / min for 4 h to obtain Pickering emulsion L-A3.

[0145] (3) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 7 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 65℃ and stir at 800 r / min for 0.5 h to obtain melamine resin prepolymer.

[0146] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A1 to adjust the pH value to 2. 0.25 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75 °C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30 °C for 5 h to obtain the pre-coated material Y-A1.

[0147] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A2 to adjust the pH value to 2. 0.55 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A2.

[0148] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A3 to adjust the pH value to 2. 0.95 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A3.

[0149] (4) Dissolve 0.032 parts by weight of chlorinated rubber in 1 part by weight of dichloromethane, add 1 part by weight of the pre-coated material Y-A1, and mix thoroughly. Add the resulting mixture to 5 parts by weight of water, stir at 500 r / min, and raise the temperature until the solvent evaporates to obtain microcapsules W-A1 with a size of 3.15-4.95 μm. The mass ratio of the core, inner wall layer and outer wall layer is 1:0.85:0.21, and the capsule wall thickness is 1.2 μm.

[0150] 0.058 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coating material Y-A2 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A2 with a size of 4.95-6.4 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.28:0.4, and the capsule wall thickness was 2.6 μm.

[0151] 0.089 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coating material Y-A3 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A3 with a size of 6.4-8.55 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.85:0.6, and the capsule wall thickness was 3.8 μm.

[0152] 0.3 parts by weight of microcapsule W-A1, 0.2 parts by weight of microcapsule W-A2, and 0.15 parts by weight of microcapsule W-A3 were mixed evenly to obtain an environmentally friendly microcapsule group.

[0153] b: Preparation of environmentally friendly asphalt:

[0154] I: Mix N-phenylmaleimide, 2,6-di-tert-butyl-p-methylphenol, tris(nonylphenol) phosphite, and 4-diethylaminobenzaldehyde in equal proportions, disperse them in 6 parts by weight of extracted oil, and further add 0.5 parts by weight of 3-aminopropyltriethoxysilane. Stir and mix at 50°C and 400 rpm for 2 hours.

[0155] II: Four parts by weight of styrene-butadiene-styrene copolymer with a relative molecular mass of 150,000, four parts by weight of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 25 wt%, and the mixture obtained in step I were kneaded in a preheated kneader at a kneading temperature of 130°C for 2 hours.

[0156] The asphalt additive was obtained by extruding at a temperature of 130℃.

[0157] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (74 1 / 10 mm penetration at 25°C) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0158] c: Mix 0.2 parts by weight of the environmentally friendly microcapsule group obtained in step a, 5 parts by weight of the environmentally friendly asphalt in the molten state at 150°C obtained in step b, and 94.8 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" after being kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain asphalt mixture.

[0159] Example 3

[0160] a: Preparation of environmentally friendly microcapsule assemblies:

[0161] (1) Preparation of barium titanate nanoparticles:

[0162] S1: Weigh 11 parts by weight of tetraethyl titanate and 10 parts by weight of ethylene glycol and add them to a flask. Stir for 2 hours at 50°C and 400 rpm to obtain a titanium precursor solution.

[0163] S2: Slowly add 10wt% ammonia water to the S1 solution until the pH of the reaction system is 11, and continue stirring at 400 rpm for 1 hour at 50℃ to obtain titanium precursor sol.

[0164] S3: Add 15.4 parts by weight of Ba(OH)2·8H2O and 15 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 3 hours at 80°C.

[0165] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 150℃, stir at 400 rpm for 36 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.

[0166] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 5 parts by weight of sodium dodecyl sulfate to 45 parts by weight of dimethylacetamide. Modify by stirring at 200 rpm for 3 hours at 140°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 50-80 nm).

[0167] (2) Add 1.3 parts by weight of cinnamaldehyde to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A1.

[0168] Add 1.3 parts by weight of tetrahydrogeraniol to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A2.

[0169] Add 1.3 parts by weight of linaloate formate to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A3.

[0170] (3) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 7 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 65℃ and stir at 800 r / min for 0.5 h to obtain melamine resin prepolymer.

[0171] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A1 to adjust the pH value to 2. 0.25 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75 °C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30 °C for 5 h to obtain the pre-coated material Y-A1.

[0172] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A2 to adjust the pH value to 2. 0.55 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A2.

[0173] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A3 to adjust the pH value to 2. 0.95 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A3.

[0174] (4) Dissolve 0.032 parts by weight of chlorinated rubber in 1 part by weight of dichloromethane, add 1 part by weight of the pre-coated material Y-A1, and mix thoroughly. Add the resulting mixture to 5 parts by weight of water, stir at 500 r / min, and raise the temperature until the solvent evaporates to obtain microcapsules W-A1 with a size of 3.0-4.8 μm. The mass ratio of the core, inner wall layer, and outer wall layer is 1:0.75:0.22, and the capsule wall thickness is 1.1 μm.

[0175] 0.058 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coating material Y-A2 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A2 with a size of 4.8-6.2 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.15:0.42, and the capsule wall thickness was 2.4 μm.

[0176] 0.089 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coating material Y-A3 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A3 with a size of 6.2-8.4 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.71:0.65, and the capsule wall thickness was 3.7 μm.

[0177] 0.3 parts by weight of microcapsule W-A1, 0.2 parts by weight of microcapsule W-A2, and 0.15 parts by weight of microcapsule W-A3 were mixed evenly to obtain an environmentally friendly microcapsule group.

[0178] b: Preparation of environmentally friendly asphalt:

[0179] I: Mix 1.8 parts by weight of N-(4-aminophenyl)maleimide, tert-butylhydroquinone, distearate pentaerythritol diphosphite, and 4-(diethylamino)salicylaldehyde in equal proportions, disperse them in 5 parts by weight of furfural refined oil, and further add 0.5 parts by weight of 3-glycidoxypropyltrimethoxysilane. Stir and mix at 50°C and 400 rpm for 2 hours.

[0180] II: Four parts by weight of styrene-butadiene-styrene copolymer with a relative molecular mass of 150,000, four parts by weight of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 25 wt%, and the mixture obtained in step I were kneaded in a preheated kneader at a kneading temperature of 130°C for 2 hours.

[0181] The asphalt additive was obtained by extruding at a temperature of 130℃.

[0182] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (74 1 / 10 mm penetration at 25°C) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0183] c: Mix 0.2 parts by weight of the environmentally friendly microcapsule group obtained in step a, 5 parts by weight of the environmentally friendly asphalt in the molten state at 150°C obtained in step b, and 94.8 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" after being kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain asphalt mixture.

[0184] Example 4

[0185] a: Preparation of environmentally friendly microcapsule assemblies:

[0186] (1) Preparation of barium titanate nanoparticles:

[0187] S1: Weigh 10 parts by weight of tetraethyl titanate and 10 parts by weight of methanol and add them to a flask. Stir for 2 hours at 35°C and 400 rpm to obtain a titanium precursor solution.

[0188] 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 35℃ to obtain titanium precursor sol.

[0189] S3: Add 13.7 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 3 hours at 80°C.

[0190] 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 37 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 8 parts by weight of 2-morpholine ethanesulfonic acid to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 35 hours at 140°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 50-80 nm).

[0192] (2) Add 1.3 parts by weight of dihydrodamasone to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A1.

[0193] Add 1.3 parts by weight of geraniol to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A2.

[0194] 1.3 parts by weight of terpine acetate were added to 8.1 parts by weight of water at 60°C, and 0.6 parts by weight of modified barium titanate nanoparticles were added. The mixture was stirred at 400 r / min for 4 h to obtain Pickering emulsion L-A3.

[0195] (3) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 7 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 65℃ and stir at 800 r / min for 0.5 h to obtain melamine resin prepolymer.

[0196] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A1 to adjust the pH value to 2. 0.25 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75 °C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30 °C for 5 h to obtain the pre-coated material Y-A1.

[0197] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A2 to adjust the pH value to 2. 0.55 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A2.

[0198] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A3 to adjust the pH value to 2. 0.95 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A3.

[0199] (4) Dissolve 0.032 parts by weight of chlorinated rubber in 1 part by weight of dichloromethane, add 1 part by weight of the pre-coated material Y-A1, and mix thoroughly. Add the resulting mixture to 5 parts by weight of water, stir at 500 r / min, and raise the temperature until the solvent evaporates to obtain microcapsules W-A1 with a size of 3.0-4.8 μm. The mass ratio of the core, inner wall layer, and outer wall layer is 1:0.75:0.22, and the capsule wall thickness is 1.1 μm.

[0200] 0.058 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coating material Y-A2 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A2 with a size of 4.8-6.2 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.15:0.42, and the capsule wall thickness was 2.4 μm.

[0201] 0.089 parts by weight of chlorinated rubber were dissolved in 1 part by weight of dichloromethane, and 1 part by weight of the pre-coating material Y-A3 was added and stirred thoroughly. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A3 with a size of 6.2-8.4 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.71:0.65, and the capsule wall thickness was 3.7 μm.

[0202] Mix 1 part by weight of microcapsule W-A1, 1 part by weight of microcapsule W-A2, and 1 part by weight of microcapsule W-A3 evenly to obtain an environmentally friendly microcapsule group.

[0203] b: Preparation of environmentally friendly asphalt:

[0204] I: Mix N-phenylmaleimide, 2,6-di-tert-butyl-p-methylphenol, tris(nonylphenol) phosphite, and 4-diethylaminobenzaldehyde in equal proportions, disperse them in 6 parts by weight of extracted oil, and further add 0.5 parts by weight of 3-aminopropyltriethoxysilane. Stir and mix at 50°C and 400 rpm for 2 hours.

[0205] II: Four parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 150,000, four parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 25 wt%, and the mixture obtained in step I were kneaded in a preheated kneader at a kneading temperature of 130°C for 2 hours and an extrusion temperature of 130°C to obtain asphalt additive.

[0206] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (74 1 / 10 mm penetration at 25°C) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0207] c: Mix 0.1 parts by weight of the environmentally friendly microcapsule group obtained in step a, 5 parts by weight of the environmentally friendly asphalt in the molten state at 150°C obtained in step b, and 94.9 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" after being kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain asphalt mixture.

[0208] Example 5

[0209] a: Preparation of environmentally friendly microcapsule assemblies:

[0210] (1) Preparation of barium titanate nanoparticles:

[0211] S1: Weigh 13 parts by weight of tetraethyl titanate and 9 parts by weight of n-butanol and add them to a flask. Stir for 2 hours at 55°C and 400 rpm to obtain a titanium precursor solution.

[0212] 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 55℃ to obtain titanium precursor sol.

[0213] S3: Add 18.5 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 3 hours at 90°C.

[0214] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 160℃, stir at 400 rpm for 35 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.

[0215] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by weight of sodium dodecylbenzenesulfonate to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 4 hours at 140°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 50-80 nm).

[0216] (2) Add 1.3 parts by weight of anisaldehyde to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A1.

[0217] Add 1.3 parts by weight of cinnamyl alcohol to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A2.

[0218] Add 1.3 parts by weight of linaloyl isobutyrate to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A3.

[0219] (3) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 7 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 65℃ and stir at 800 r / min for 0.5 h to obtain melamine resin prepolymer.

[0220] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A1 to adjust the pH value to 2. 0.25 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75 °C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30 °C for 5 h to obtain the pre-coated material Y-A1.

[0221] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A2 to adjust the pH value to 2. 0.55 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A2.

[0222] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A3 to adjust the pH value to 2. 0.95 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A3.

[0223] (4) Dissolve 0.032 parts by weight of styrene-butadiene rubber in 1.5 parts by weight of trichloroethylene, add 1 part by weight of the pre-coating material Y-A1, and mix thoroughly. Add the resulting mixture to 5 parts by weight of water, stir at 500 r / min, and raise the temperature until the solvent evaporates to obtain microcapsules W-A1 with a size of 3.0-4.8 μm. The mass ratio of the core, inner wall layer, and outer wall layer is 1:0.75:0.22, and the capsule wall thickness is 1.1 μm.

[0224] 0.058 parts by weight of styrene-butadiene rubber was dissolved in 1.5 parts by weight of trichloroethylene, and 1 part by weight of the pre-coating material Y-A2 was added and thoroughly mixed. The resulting mixture was added to 5 parts by weight of water and stirred at 500 r / min. The temperature was increased until the solvent evaporated to obtain microcapsules W-A2 with a size of 4.8-6.2 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.15:0.42, and the capsule wall thickness was 2.5 μm.

[0225] 0.089 parts by weight of styrene-butadiene rubber was added to 1.5 parts by weight of trichloroethylene, along with 1 part by weight of the pre-coating material Y-A3, and the mixture was stirred thoroughly. The resulting mixture was then added to 5 parts by weight of water and stirred at 500 rpm. The temperature was increased until the solvent evaporated, yielding microcapsules W-A3 with a size of 6.2-8.4 μm. The mass ratio of the core, inner wall layer, and outer wall layer was 1:1.71:0.65, and the capsule wall thickness was 3.8 μm.

[0226] 0.3 parts by weight of microcapsule W-A1, 0.2 parts by weight of microcapsule W-A2, and 0.15 parts by weight of microcapsule W-A3 were mixed evenly to obtain an environmentally friendly microcapsule group.

[0227] b: Preparation of environmentally friendly asphalt:

[0228] I: Mix 2 parts by weight of 4-maleimide phenol, 2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol, tris(nonylphenol) phosphite, and N,N-diethyl-p-aminobenzaldehyde in equal proportions, disperse them in 6 parts by weight of extracted oil, and further add 0.5 parts by weight of 3-aminopropyltriethoxysilane. Stir and mix at 50°C and 400 rpm for 2 hours.

[0229] II: Four parts by weight of styrene-butadiene-styrene copolymer with a relative molecular mass of 150,000, four parts by weight of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 25 wt%, and the mixture obtained in step I were kneaded in a preheated kneader at a kneading temperature of 130°C for 2 hours.

[0230] The asphalt additive was obtained by extruding at a temperature of 130℃.

[0231] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (74 1 / 10 mm penetration at 25°C) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0232] c: Mix 0.2 parts by weight of the environmentally friendly microcapsule group obtained in step a, 5 parts by weight of the environmentally friendly asphalt in the molten state at 150°C obtained in step b, and 94.8 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" after being kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain asphalt mixture.

[0233] Comparative Example 1

[0234] Five parts by weight of molten base asphalt at 150°C (penetration 74 1 / 10 mm at 25°C) 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°C for 1.5 minutes to obtain asphalt mixture.

[0235] Comparative Example 2

[0236] a: Preparation of environmentally friendly asphalt:

[0237] I: Mix N-phenylmaleimide, 2,6-di-tert-butyl-p-methylphenol, tris(nonylphenol) phosphite, and 4-diethylaminobenzaldehyde in equal proportions, disperse them in 6 parts by weight of extracted oil, and further add 0.5 parts by weight of 3-aminopropyltriethoxysilane. Stir and mix at 50°C and 400 rpm for 2 hours.

[0238] II: Four parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 150,000, four parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 25 wt%, and the mixture obtained in step I were kneaded in a preheated kneader at a kneading temperature of 130°C for 2 hours and an extrusion temperature of 130°C to obtain asphalt additive.

[0239] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (74 1 / 10 mm penetration at 25°C) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0240] b: Mix 5 parts by weight of the environmentally friendly asphalt obtained in step a 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.

[0241] Comparative Example 3

[0242] a: Preparation of environmentally friendly microcapsule assemblies:

[0243] (1) Preparation of barium titanate nanoparticles:

[0244] S1: Weigh 15 parts by weight of tetraethyl titanate and 10 parts by weight of anhydrous ethanol and add them to a flask. Stir for 2 hours at 60°C and 400 rpm to obtain a titanium precursor solution.

[0245] 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.

[0246] S3: Add 21 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 3 hours at 80°C.

[0247] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 160℃, stir at 400 rpm for 35 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.

[0248] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by weight of sodium dodecylbenzenesulfonate to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 4 hours at 140°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 50-80 nm).

[0249] (2) Add 1.3 parts by weight of anisaldehyde to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A1.

[0250] Add 1.3 parts by weight of cinnamyl alcohol to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A2.

[0251] Add 1.3 parts by weight of linaloyl isobutyrate to 8.1 parts by weight of water at 60°C, add 0.6 parts by weight of modified barium titanate nanoparticles, and stir at 400 r / min for 4 h to obtain Pickering emulsion L-A3.

[0252] (3) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 7 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 65℃ and stir at 800 r / min for 0.5 h to obtain melamine resin prepolymer.

[0253] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A1 to adjust the pH value to 2. 0.25 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75 °C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30 °C for 5 h to obtain the pre-coated material Y-A1.

[0254] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A2 to adjust the pH value to 2. 0.55 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A2.

[0255] Dilute hydrochloric acid was added dropwise to 1 part by weight of Pickering emulsion L-A3 to adjust the pH value to 2. 0.95 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the Pickering emulsion. The mixture was stirred at 700 r / min and reacted at 75°C for 2 h. The solid powder in the reaction system was then filtered and washed, and vacuum dried at -30°C for 5 h to obtain the pre-coated material Y-A3.

[0256] 0.3 parts by weight of pre-coating material Y-A1, 0.2 parts by weight of pre-coating material Y-A2, and 0.15 parts by weight of pre-coating material Y-A3 were mixed evenly to obtain an environmentally friendly microcapsule assembly.

[0257] b: Preparation of environmentally friendly asphalt:

[0258] I: Mix N-phenylmaleimide, 2,6-di-tert-butyl-p-methylphenol, tris(nonylphenol) phosphite, and 4-diethylaminobenzaldehyde in equal proportions, disperse them in 6 parts by weight of extracted oil, and further add 0.5 parts by weight of 3-aminopropyltriethoxysilane. Stir and mix at 50°C and 400 rpm for 2 hours.

[0259] II: Four parts by weight of styrene-butadiene-styrene copolymer with a relative molecular mass of 150,000, four parts by weight of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 25 wt%, and the mixture obtained in step I were kneaded in a preheated kneader at a kneading temperature of 130°C for 2 hours.

[0260] The asphalt additive was obtained by extruding at a temperature of 130℃.

[0261] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (74 1 / 10 mm penetration at 25°C) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0262] c: Mix 0.2 parts by weight of the environmentally friendly microcapsule group obtained in step a, 5 parts by weight of the environmentally friendly asphalt in the molten state at 150°C obtained in step b, and 94.8 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" after being kept at 160°C for 4 hours. Mix at 148°C for 1.5 minutes to obtain asphalt mixture.

[0263] Test Example 1

[0264] Hydrogen sulfide and volatile organic compounds are the main causes of the pungent odor of asphalt mixture fumes. Asphalt mixture samples prepared in Examples 1-5 and Comparative Examples 1-3 were stored at 158°C for 10 hours to simulate long-distance transportation of asphalt mixtures. Then, an equal mass of the stored asphalt mixture was transferred to an asphalt fume enrichment and collection device for fume enrichment. The enrichment temperature was set at 148°C and the enrichment time was 8 hours. After enrichment, the gas in the sealed container was extracted and tested. The data obtained are shown in Table 1 below.

[0265] Table 1

[0266]

[0267] Test Example 2

[0268] Using the Los Angeles abrasion tester manufactured by Beijing High-speed Railway Construction Technology Development Co., Ltd., the anti-stripping performance of asphalt mixtures was evaluated using the test method specified in "T0733—2011 Kentaburg Asphalt Mixture Stripping Test" of the Ministry of Transport's "JTGE20—2011 Highway Engineering Asphalt and Asphalt Mixture Test Procedure". The obtained data are shown in Table 2 below.

[0269] Table 2

[0270] Test sample Mixture loss rate, % Example 1 4.00 Example 2 5.88 Example 3 4.70 Example 4 8.70 Example 5 4.51 Comparative Example 1 23.50 Comparative Example 2 16.22 Comparative Example 3 19.74

[0271] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, 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, By weight, it includes the following components: Graded stone: 93-95.9 parts per unit area; Environmentally friendly microcapsule group: 0.1-1 part, preferably 0.2-1 part; Environmentally friendly asphalt: 4-6 parts; The environmentally friendly microcapsule assembly includes a first microcapsule, a second microcapsule, and a third microcapsule. Each of the first, second, and third microcapsules includes a core and a wall. The core is encapsulated within the wall and contains an active component. The wall includes an inner wall layer and an outer wall layer. The inner wall layer is a barium titanate resin composite wall, and the outer wall layer is a rubber material.

2. The asphalt mixture according to claim 1, characterized in that, The first microcapsule has a wall thickness of 0.6–2.2 μm; the second microcapsule has a wall thickness greater than 2.2 μm and less than 3.3 μm; and the third microcapsule has a wall thickness of 3.3–5.2 μm. And / or, in the environmentally friendly microcapsules, the mass ratio of the first microcapsule, the second microcapsule, and the third microcapsule is 1:(0.2-5):(0.2-5), preferably 1:(0.2-0.8):(0.2-0.8). And / or, in the first microcapsule, the mass ratio of the core, inner wall layer, and outer wall layer is 1:(0.7-1):(0.2-0.5); in the second microcapsule, the mass ratio of the core, inner wall layer, and outer wall layer is 1:(1.1-1.5):(0.4-0.7); and in the third microcapsule, the mass ratio of the core, inner wall layer, and outer wall layer is 1:(1.7-2):(0.5-1). And / or, the size of the first microcapsule, the second microcapsule and the third microcapsule is each independently 50 μm or less, preferably 20 μm or less, more preferably 3-15 μm.

3. The asphalt mixture according to claim 1, characterized in that, The barium titanate resin composite wall has a resin to barium titanate mass ratio of (0.1-8):

1. And / or, the barium titanate is a nanoparticle with a particle size of 20-100 nm; And / or, the resin is at least one of melamine resin, urea-formaldehyde resin and polymethyl methacrylate, preferably melamine resin; And / or, the rubber material is at least one of chlorinated rubber, styrene-butadiene rubber, and chloroprene rubber.

4. The asphalt mixture according to claim 1, characterized in that, The active component is an inhibitor for suppressing the release of asphalt fumes, preferably at least one of aldehydes, alcohols, phenols, and esters; preferably, the active component in the first microcapsule is selected from aldehydes and / or ketones, the active component in the second microcapsule is selected from alcohols, and the active component in the third microcapsule is selected from esters.

5. The asphalt mixture according to claim 1, characterized in that, The environmentally friendly asphalt, by weight, comprises the following components: Odor-neutralizing active substance: 0.05-10 parts; Dispersant: 1-20 parts; Silane coupling agent: 0.1-10 parts Styrene-butadiene-styrene polymer: 1-20 parts, preferably 4-8 parts; Ethylene-vinyl acetate copolymer: 1-20 parts, preferably 4-8 parts; Base bitumen: 50-500 parts.

6. The asphalt mixture according to claim 5, characterized in that, The deodorizing active substance 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 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.

7. A method for preparing asphalt mixture according to any one of claims 1-6, comprising: a: Preparation of environmentally friendly microcapsule assemblies; b: Prepare environmentally friendly asphalt and heat it to melt; c: Mix the environmentally friendly microcapsule group obtained in step a, the environmentally friendly asphalt in the molten state in step b, and the graded stone materials to obtain an asphalt mixture.

8. The method according to claim 7, characterized in that, Step a method for preparing an environmentally friendly microcapsule assembly includes: mixing a first microcapsule, a second microcapsule, and a third microcapsule evenly to obtain an environmentally friendly microcapsule assembly; The preparation methods of the first microcapsule, the second microcapsule, and the third microcapsule each independently include: (1) Preparation of barium titanate nanoparticles; (2) Mix the active component, barium titanate nanoparticles and water to form a Pickering emulsion; (3) The Pickering emulsion is reacted with the resin prepolymer, then filtered, washed and freeze-dried to obtain the pre-coated material; (4) Mix the rubber material, solvent and the pre-coated material, then mix the resulting mixture with water, stir and heat to obtain microcapsules.

9. The method according to claim 8, 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.

10. The method according to claim 9, 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 is more preferably tetraethyl 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.

11. The method according to claim 9, 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.

12. The method according to claim 9, 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.

13. The method according to claim 9, 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.

14. The method according to claim 9, 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.

15. The method according to claim 8, characterized in that, In step (2), the mass ratio of the active component, barium titanate nanoparticles and water is 1:(0.1-0.8):(5-20); And / or, in step (2), the mixing is carried out under stirring, the stirring speed is 200-500 rpm, the stirring time is 2-5 hours, and the temperature is 35-65℃.

16. The method according to claim 8, characterized in that, In step (3), before the Pickering emulsion reacts with the resin prepolymer, the pH value of the Pickering emulsion is adjusted to below 5, preferably 2-4; And / or, in step (3), the reaction between the Pickering emulsion and the resin prepolymer is carried out under stirring at a speed of 400-800 rpm, a reaction temperature of 60-90°C, and a time of 1-5 hours. And / or, in step (3), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

17. The method according to claim 8, characterized in that, In step (4), the mass ratio of the rubber material, the solvent, and the water is 1:(10-200):(10-300); And / or, in step (4), the solvent is a volatile solvent selected from at least one of carbon tetrachloride, dichloromethane and trichloroethylene; And / or, in step (4), the stirring speed is 200-800 rpm.

18. The method according to claim 7, characterized in that, Step b, the preparation method for environmentally friendly asphalt, includes: I: Heat and stir the odor-neutralizing active ingredient, silane coupling agent, and dispersant together; 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: After mixing the asphalt additive obtained in step II with the molten base asphalt, an environmentally friendly asphalt is obtained.

19. The method according to claim 18, characterized in that, In step I, the stirring speed is 200-500 rpm; the stirring temperature is 30-80℃; and the stirring time is 1-4 hours. And / or, in step II, the mixing conditions are: mixing temperature of 100-160℃, mixing time of 0.5-2h; and extrusion temperature of 100-160℃. And / or, in step III, the temperature at which the base asphalt is heated to a molten state is 133-163°C; And / or, the stirring speed is 400-600 rpm, and environmentally friendly high-performance asphalt can be obtained after stirring for 1-4 hours.

20. The method according to claim 7, 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 mixing conditions are: mixing temperature of 133-163℃ and mixing time of 0.5min-3min.

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