Environment-friendly asphalt mixture and preparation method thereof

Abstract

The application discloses an environment-friendly asphalt mixture and a preparation method thereof. The environment-friendly asphalt mixture comprises the following components in parts by weight: 4-6 parts of environment-friendly asphalt; 0.1-1 parts of environment-friendly microcapsules; and 93-95.9 parts of graded stones. The environment-friendly microcapsules comprise a composite shell material and a core material. The composite shell material comprises an inorganic base shell, barium titanate nanoparticles, polydopamine and cuprous oxide. The core material comprises a deodorant. Compared with common asphalt mixtures, the environment-friendly asphalt mixture not only has a greatly reduced asphalt smoke emission, but also has a relatively strong road performance.

Description

Technical Field

[0001] This invention belongs to the field of environmentally friendly asphalt, and specifically relates to an environmentally friendly asphalt mixture and its preparation method. Background Technology

[0002] Asphalt pavement, as an important component of transportation infrastructure, utilizes a hot-mix, hot-lay process during its production. While highly efficient, this process involves the emission of large amounts of harmful fumes, posing a threat to the environment, ecosystems, and public health. These fumes contain various toxic and harmful substances, such as potent carcinogens like polycyclic aromatic hydrocarbons (PAHs), as well as irritating gases like ammonia and hydrogen sulfide; their impact cannot be ignored.

[0003] Given the Chinese government's strong emphasis on environmental protection and green development, more restrictive policies targeting asphalt fume emissions are expected to be introduced in the future. Against this backdrop, warm-mix asphalt technology, as an attempt to reduce emissions by lowering construction temperatures, faces challenges in practical application, including impacting pavement performance and incurring high costs.

[0004] CN111747685A discloses an environmentally friendly, odor-free asphalt mixture and its preparation method. This method involves adding large-sized adsorbents such as rice husk powder to the asphalt mixture to adsorb asphalt fumes. Although this method can reduce the release of asphalt fumes to a certain extent, it inevitably damages the performance of asphalt pavement.

[0005] Therefore, in order to balance the relationship between transportation construction and environmental protection, there is an urgent need to develop more economical, efficient, and environmentally friendly asphalt fume emission reduction technologies. This is not only a proactive response to current environmental problems, but also an important exploration of a future path to sustainable development. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides an environmentally friendly asphalt mixture and its preparation method. Compared with ordinary asphalt mixtures, the environmentally friendly asphalt mixture of this invention not only significantly reduces asphalt fume emissions but also has superior road performance.

[0007] The first aspect of this invention provides an environmentally friendly asphalt mixture, comprising the following components by weight:

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

[0009] Environmentally friendly microcapsules: 0.1-1 part, preferably 0.3-0.8 parts;

[0010] Graded stone: 93-95.9 parts per unit area;

[0011] The environmentally friendly microcapsule comprises a composite shell and a core material. The composite shell includes an inorganic base shell, barium titanate nanoparticles, polydopamine, and cuprous oxide. The core material includes a neutralizing agent.

[0012] 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".

[0013] Furthermore, the particle size of the environmentally friendly microcapsules is 1-10 μm.

[0014] Furthermore, the mass ratio of the composite shell material to the core material is 1:(0.2-2).

[0015] Furthermore, the odor neutralizer is one or more of aldehydes, alcohols, esters, and alkenes, preferably including aldehydes, alcohols, esters, and alkenes simultaneously.

[0016] Further, the aldehydes are selected from one or more aromatic aldehydes with a molecular weight greater than 120 and cyclic terpene aldehydes with a molecular weight greater than 170. The aromatic aldehydes with a molecular weight greater than 120 are selected from one or more of cinnamaldehyde, jasmine aldehyde, vanillin, neojasmine aldehyde, and methylpentylcinnamaldehyde; the cyclic terpene aldehydes with a molecular weight greater than 170 are selected from one or more of crocinnamaldehyde and β-cyclocitral.

[0017] Further, the alcohols are selected from one or more of terpenols with a molecular weight greater than 140 and cyclic terpenols with a molecular weight greater than 150. The terpenols with a molecular weight greater than 140 are selected from one or more of geraniol, linalool, citronellol, nerol, tetrahydrogeraniol, nerolidol, and 3,7-dimethyl-octen-2-ol; the cyclic terpenols with a molecular weight greater than 150 are selected from one or more of neomenthol, α-terpineol, borneol, vetiverol, and santalol.

[0018] Further, the esters are selected from one or more of fatty acid esters with a molecular weight greater than 130 and salicylate esters with a molecular weight greater than 200. The fatty acid esters with a molecular weight greater than 130 are selected from one or more of isoamyl acetate, leaf ester acetate, butyl butyrate, ethyl hexanoate, methyl laurate, and methyl 2-octynoate; the salicylate esters with a molecular weight greater than 200 are selected from one or more of isoamyl salicylate, leaf ester salicylate, and benzyl salicylate.

[0019] Further, the alkene is selected from cyclic terpenes with a molecular weight greater than 130. Preferably, it is selected from one or more of limonene, α-terpinene, α-phellandrene, α-pinene, thujone, juniperene, and longleafene.

[0020] Furthermore, 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 barium titanate nanoparticles, polydopamine, and cuprous oxide is 1:(0.2-0.8):(0.1-0.5):(0.5-2).

[0021] Furthermore, the inorganic base shell is made of at least one material selected from silicon dioxide and titanium dioxide, preferably silicon dioxide.

[0022] Furthermore, the environmentally friendly asphalt, by weight, comprises the following components:

[0023] Odor-neutralizing active ingredient: 0.05-10 parts;

[0024] Dispersant: 1-20 parts;

[0025] Silane coupling agent: 0.1-10 parts;

[0026] Amide compounds: 0.1-10 parts;

[0027] Styrene-butadiene-styrene polymer: 1-20 parts, preferably 4-8 parts;

[0028] Ethylene-vinyl acetate copolymer: 1-20 parts, preferably 3-7 parts;

[0029] Base bitumen: 50-500 parts.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] Furthermore, the dispersant is one or more of the following: extracted oil, furfural refined oil, and catalytic cracking slurry.

[0035] Furthermore, the silane coupling agent is selected from one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane-3-glycidyl etheroxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0036] Furthermore, the amide compound is selected from higher fatty acid amides with more than 18 carbon atoms, preferably selected from one or more of oleamide, erucamide, oleyl palmitamide, and docosamide.

[0037] Furthermore, the styrene-butadiene-styrene copolymer is linear and / or star-shaped, with an average relative molecular mass of 100,000 to 300,000.

[0038] 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.

[0039] Furthermore, the penetration of the base asphalt at 25°C is 30-210 1 / 10 mm.

[0040] A second aspect of this invention provides a method for preparing the above-mentioned environmentally friendly asphalt mixture, comprising:

[0041] a: Preparation of environmentally friendly microcapsules;

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

[0043] c: Mix the environmentally friendly microcapsules obtained in step a, the environmentally friendly asphalt in the molten state of step b, and the graded aggregate to obtain an asphalt mixture.

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

[0045] (1) Preparation of barium titanate nanoparticles;

[0046] (2) Stir and mix one or more deodorizing agents to obtain a core material mixture;

[0047] (3) The core material mixture and barium titanate nanoparticles are stirred and mixed in a solvent;

[0048] (4) Add the inorganic base shell precursor to the reaction system of step (3), stir and mix to obtain Pickering emulsion;

[0049] (5) Adjust the pH value of the Pickering emulsion obtained in step (4), continue stirring, then age, filter, freeze dry, and obtain an environmentally friendly microcapsule matrix;

[0050] (6) Disperse the environmentally friendly microcapsule matrix obtained in step (5) in a buffer solution, add dopamine hydrochloride, process with stirring, then filter, wash, freeze dry to obtain solid particles;

[0051] (7) Add the solid particles and copper ion solution obtained in step (6) into the reaction vessel and carry out the reaction with stirring;

[0052] (8) Mix the reducing agent with the buffer solution, stir to dissolve, and then add it to the reaction system of step (7). Stir to carry out the reaction, then filter, wash, freeze dry, and obtain environmentally friendly microcapsules.

[0053] Furthermore, the method for preparing barium titanate nanoparticles in step (1) includes:

[0054] S1: Stir and mix the titanium precursor and solvent;

[0055] S2: Adjust the pH of the mixed solution obtained in S1 and stir until a titanium precursor sol is obtained;

[0056] S3: Mix the barium precursor with water;

[0057] 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.

[0058] 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.

[0059] Further, in step S1, the titanium precursor is selected from at least one of tetraethyl titanate, n-propyl titanate, and tetrabutyl titanate.

[0060] 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.

[0061] 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.

[0062] Further, in step S1, the mass ratio of the titanium precursor to the solvent is (1-20):1.

[0063] Further, in step S2, the pH of the S1 mixed solution is adjusted to pH = 9-12.

[0064] 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.

[0065] 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.

[0066] Further, in step S3, the barium precursor is at least one of Ba(OH)2, Ba(OH)2·H2O, and Ba(OH)2·8H2O.

[0067] 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.

[0068] 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.

[0069] 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).

[0070] 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.

[0071] Furthermore, in step S4, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0072] Furthermore, in step S4, the grinding specifically means grinding until there are no obvious lumps.

[0073] Furthermore, in step S5, the diameter of the barium titanate nanoparticles is 20-100 nm.

[0074] Further, in step S5, the surfactant is a cationic surfactant, preferably at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] Furthermore, in step S5, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0079] Furthermore, in step (2), the stirring speed is 400-600 rpm, the stirring temperature is 30-70℃, and the stirring time is 3-10 minutes.

[0080] Further, in step (3), the solvent is an aprotic solvent with a boiling point >100℃, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide.

[0081] Further, in step (3), the mass ratio of the solvent to the barium titanate nanoparticles is (10-40):1.

[0082] Furthermore, in step (3), the stirring speed is 400-600 rpm, the stirring temperature is 30-60℃, and the stirring time is 4-6 hours.

[0083] Further, in step (4), 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 at least one of methyl silicate, ethyl orthosilicate, tetraethyl orthosilicate, and butyl orthosilicate.

[0084] Furthermore, in step (4), the stirring speed is 400-600 rpm, the stirring temperature is 30-60℃, and the stirring time is 4-6 hours.

[0085] Further, in step (5), the pH is adjusted to 3-6. The pH can be adjusted using a dilute acid, such as dilute hydrochloric acid. The stirring speed is 400-600 rpm, the stirring temperature is 30-60℃, and the stirring time is 4-6 hours.

[0086] Further, in step (5), the aging conditions are: standing at 40-60℃ for 12-30 hours. The freeze-drying conditions are: vacuum drying at -40 to -20℃ for 4-8 hours.

[0087] Further, in step (6), the buffer solution is at least one of phosphate buffer, carbonate buffer, and tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer), preferably tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer).

[0088] Furthermore, in step (6), the pH value of the buffer solution is preferably 8-10.

[0089] Further, in step (6), the mass ratio of the buffer solution to the environmentally friendly microcapsule matrix obtained in step (5) is (10-100):1.

[0090] Furthermore, in step (6), after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

[0091] Furthermore, in step (6), the stirring speed is 100-300 rpm, the stirring temperature is 20-40℃, and the stirring time is 12-24 hours.

[0092] Furthermore, in step (6), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0093] Further, in step (7), the copper ion solution is prepared by mixing copper ion salt and deionized water, and the copper ion salt is preferably anhydrous copper sulfate.

[0094] Further, in step (7), the concentration of copper ions in the copper ion solution is 0.05-0.5 mol / L.

[0095] Further, in step (7), the mass ratio of the solid particles and copper ion solution obtained in step (6) is 1:(50-200).

[0096] Furthermore, in step (7), the stirring speed is 100-450 rpm, the reaction temperature is 100-190℃, and the reaction time is 1-5 hours.

[0097] Further, in step (8), the reducing agent is a sulfite reducing agent, preferably selected from at least one of potassium sulfite and sodium sulfite.

[0098] Further, in step (8), the buffer solution is selected from at least one of acetate buffer and phosphate buffer, preferably acetate buffer; the pH value of the buffer solution is 4.5-6.5.

[0099] Further, in step (8), the mass ratio of the reducing agent to the buffer solution is 1:(10-20).

[0100] Furthermore, in step (8), 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.

[0101] Furthermore, in step (8), when the reaction is carried out under stirring, the stirring speed is 100-450 rpm, the reaction temperature is 60-95℃, and the reaction time is 2-5 hours.

[0102] Further, in step (8), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0103] Furthermore, step b, the method for preparing environmentally friendly asphalt, includes:

[0104] I: Heat and stir to mix the odor-neutralizing active ingredient, silane coupling agent, dispersant, and amide compound;

[0105] 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;

[0106] III: After mixing the asphalt additive obtained in step II with the molten base asphalt, an environmentally friendly asphalt is obtained.

[0107] 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.

[0108] 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℃.

[0109] Furthermore, in step III, the base asphalt is heated to a molten state at a temperature of 133-163°C, and the stirring speed is 400-600 rpm. After stirring for 1-4 hours, environmentally friendly high-performance asphalt can be obtained.

[0110] Furthermore, in step c, the environmentally friendly asphalt is heated to a melting temperature of 133℃-163℃.

[0111] 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.

[0112] Further, in step c, the mixing conditions are: mixing temperature of 133-163℃ and mixing time of 0.5min-5min.

[0113] Compared with the prior art, the present invention has the following advantages:

[0114] (1) The environmentally friendly asphalt of the present invention, based on the role of silane coupling agent, styrene-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, odor-neutralizing active substance and amide compound can be fused in the melting and extrusion process to obtain an environmentally friendly high-performance asphalt additive. After being added to asphalt, the 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 mixture.

[0115] (2) The environmentally friendly microcapsule of the present invention has a composite shell material comprising 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 the asphalt mixing and construction process, the high temperature attracts compounds released by the 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 released by the microcapsules to react with more of the above compounds, thereby effectively reducing the impact of irritating gases released from asphalt pavements on the human body.

[0116] (3) The environmentally friendly microcapsule of the present invention has a composite shell material comprising an inorganic base shell, barium titanate nanoparticles, polydopamine and 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 during the production and construction of asphalt mixtures. 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 very large specific surface area on the surface of the microcapsule, which effectively improves the adsorption capacity of cuprous oxide for various 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 released by the microcapsule and various pollutants in the asphalt fumes, further enhancing the smoke-suppressing ability of the environmentally friendly microcapsule.

[0117] (4) The environmentally friendly asphalt mixture of the present invention incorporates environmentally friendly microcapsules, which encapsulate low-boiling-point odor-neutralizing active components in a composite shell. These active components can be slowly released from the microcapsules during asphalt construction and undergo nucleophilic reactions with compounds in the asphalt that have irritating odors to generate compounds with higher stability and boiling points. These compounds are difficult to decompose and volatilize during high-temperature construction of the asphalt mixture, thereby reducing the irritating odor of asphalt fumes. At the same time, microencapsulating the odor-neutralizing active components can also effectively prevent them from reacting in time due to rapid volatilization at high temperatures. This not only prolongs the action time of the odor-neutralizing active components but also further improves their safety in use.

[0118] (5) The environmentally friendly asphalt mixture of the present invention, when incorporated into the mixture as a mineral powder component, can effectively improve the bonding strength between asphalt and aggregate and improve the road performance of the asphalt mixture. Detailed Implementation

[0119] To further illustrate the technical solution of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0120] 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.

[0121] The benzene series compounds in the asphalt flue gas described in this invention are tested according to the solid adsorption thermal desorption-gas chromatography method for the determination of benzene series compounds in ambient air, as specified in HJ 583-2010.

[0122] 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.

[0123] Example 1

[0124] a: Preparation of environmentally friendly microcapsules:

[0125] (1): Preparation of barium titanate nanoparticles:

[0126] S1: Weigh 20 parts by weight of tetrapropyl titanate and 15 parts by weight of anhydrous ethanol and add them to a flask. Stir for 1 hour at 45°C and 400 rpm to obtain a titanium precursor solution.

[0127] 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 45℃ to obtain titanium precursor sol.

[0128] S3: Add 17.8 parts by weight of Ba(OH)2·8H2O and 18 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 85°C.

[0129] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 145℃, stir at 400 rpm for 25 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.

[0130] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by weight of hexadecyltrimethylammonium bromide to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 4 hours at 150°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 40-60 nm).

[0131] (2): Mix jasmine aldehyde, linalool, ethyl hexanoate and limonene in equal weight ratios, and stir at 400 rpm for 10 minutes at 50°C to obtain core material mixture.

[0132] (3): 4.5 parts by weight of the core material mixture obtained in step (2), 1.8 parts by weight of the barium titanate nanoparticles obtained in step (1) and 35 parts by weight of dimethylacetamide were stirred at 350 rpm for 4.5 hours at 55°C.

[0133] (4): Add methyl silicate to the reaction system of step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 9:5. Continue stirring at 400 rpm for 5 hours at 55°C to obtain Pickering emulsion.

[0134] (5): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (4) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 400 rpm for 5.5 hours at 55°C. Stop stirring and age for 24 hours while keeping the temperature constant. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0135] (6): The environmentally friendly microcapsule matrix obtained in step (5) was added to a Tris buffer solution with a pH of 8.5. The mass ratio of the Tris buffer solution to the deodorizing environmentally friendly microcapsule matrix was 60:1. Then, dopamine hydrochloride was added to make the concentration of dopamine in the reaction system 6 mg / mL. The mixture was stirred at 200 rpm for 12 hours at 25°C. The stirring was then stopped. The bottom solid powder was filtered and washed, and then vacuum dried at -30°C for 5 hours.

[0136] (7): Mix 1 part by weight of anhydrous copper sulfate and 50 parts by weight of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by weight of the solid particles obtained after drying in step (6) and the copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 hour at 110°C.

[0137] (8): Add 3.5 parts by weight of potassium sulfite to 50 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 60 °C. Add the resulting mixed solution to the reaction vessel (7), close the lid, and stir at 200 rpm for 4 h at 90 °C. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30 °C for 5 h to obtain environmentally friendly microcapsules with a particle size of 3.07~7.81 μm.

[0138] b: Preparation of environmentally friendly asphalt:

[0139] I: Mix N-(4-aminophenyl)maleimide, 2-tert-butyl-p-cresol, tris(2-cyclohexylphenyl)phosphite, and 4-(diethylamino)salicylaldehyde in equal proportions, and disperse them in 5 parts by weight of catalytic cracking slurry. Then add 0.5 parts by weight of 3-aminopropyltriethoxysilane and 0.5 parts by weight of oleamide, and stir and mix at 50°C and 400 rpm for 2 hours.

[0140] II: 4.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 200,000, 3.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 23 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 140°C for 1.5 h and an extrusion temperature of 140°C to obtain asphalt additive;

[0141] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 71 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0142] c: Mix 0.3 parts by weight of the environmentally friendly 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 94.7 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.

[0143] Example 2

[0144] a: Preparation of environmentally friendly microcapsules:

[0145] (1): Preparation of barium titanate nanoparticles:

[0146] S1: Weigh 16 parts by weight of n-propyl titanate and 14 parts by weight of n-butanol and add them to a flask. Stir at 55°C and 400 rpm for 2 hours to obtain a titanium precursor solution.

[0147] 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 55℃ to obtain titanium precursor sol.

[0148] S3: Add 14.2 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 85°C.

[0149] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 145℃, stir at 400 rpm for 25 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.

[0150] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by weight of octadecyltrimethylammonium chloride to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 4 hours at 150°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 40-60 nm).

[0151] (2): Mix pentylcinnamaldehyde and α-terpineol in equal weight ratios, and stir at 400 rpm for 10 minutes at 50°C to obtain core material mixture;

[0152] (3): 4.8 parts by weight of the core material mixture obtained in step (2), 1.8 parts by weight of the barium titanate nanoparticles obtained in step (1) and 35 parts by weight of dimethylphosphoramide were stirred at 350 rpm for 4.5 hours at 55°C.

[0153] (4): Add methyl silicate to the reaction system of step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 9:5. Continue stirring at 400 rpm for 5 hours at 55°C to obtain Pickering emulsion.

[0154] (5): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (4) using a peristaltic pump until the pH of the reaction system is 4.0. Continue stirring at 400 rpm for 5 hours at 50°C, then stop stirring and age for 24 hours at the same temperature. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0155] (6): The environmentally friendly microcapsule matrix obtained in step (5) was added to a Tris buffer solution with a pH of 8.5. The mass ratio of the Tris buffer solution to the deodorizing environmentally friendly microcapsule matrix was 60:1. Then, dopamine hydrochloride was added to make the concentration of dopamine in the reaction system 6 mg / mL. The mixture was stirred at 200 rpm for 12 hours at 25°C. The stirring was then stopped. The bottom solid powder was filtered and washed, and then vacuum dried at -30°C for 5 hours.

[0156] (7): Mix 1 part by weight of anhydrous copper sulfate and 50 parts by weight of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by weight of the solid particles obtained after drying in step (6) and the copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 hour at 110°C.

[0157] (8): Add 3.5 parts by weight of potassium sulfite to 50 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 60 °C. Add the resulting mixed solution to the reaction vessel (7), close the lid, and stir at 200 rpm for 4 h at 90 °C. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30 °C for 5 h to obtain environmentally friendly microcapsules with a particle size of 3.12~7.96 μm.

[0158] b: Preparation of environmentally friendly asphalt:

[0159] I: Mix N-(4-aminophenyl)maleimide, 2-tert-butyl-p-cresol, tris(2-cyclohexylphenyl)phosphite, and 4-(diethylamino)salicylaldehyde in equal proportions, and disperse them in 5 parts by weight of catalytic cracking slurry. Then add 0.5 parts by weight of 3-aminopropyltriethoxysilane and 0.5 parts by weight of oleamide, and stir and mix at 50°C and 400 rpm for 2 hours.

[0160] II: 4.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 200,000, 3.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 23 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 140°C for 1.5 h and an extrusion temperature of 140°C to obtain asphalt additive;

[0161] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 71 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0162] c: Mix 0.3 parts by weight of the environmentally friendly 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 94.7 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.

[0163] Example 3

[0164] a: Preparation of environmentally friendly microcapsules:

[0165] (1): Preparation of barium titanate nanoparticles:

[0166] S1: Weigh 18 parts by weight of tetrapropyl titanate and 14 parts by weight of butanediol and add them to a flask. Stir at 55°C and 400 rpm for 1 hour to obtain a titanium precursor solution.

[0167] S2: Slowly add 10wt% ammonia water 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.

[0168] S3: Add 16 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 85°C.

[0169] 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 24 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.

[0170] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by weight of dodecyl dimethyl benzyl ammonium chloride to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 4 hours at 150°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 40-60 nm).

[0171] (2): Cinnamaldehyde, nerolidol, butyl butyrate, and α-terpinene are mixed in equal weight ratios and stirred at 400 rpm for 10 minutes at 50°C to obtain a core material mixture.

[0172] (3): 4.5 parts by weight of the core material mixture obtained in step (2), 1.8 parts by weight of the barium titanate nanoparticles obtained in step (1) and 35 parts by weight of dimethylacetamide were stirred at 350 rpm for 4.5 hours at 55°C.

[0173] (4): Add tetraethyl orthosilicate to the reaction system of step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 9:5. Continue stirring at 400 rpm for 5 hours at 55°C to obtain Pickering emulsion.

[0174] (5): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (4) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 400 rpm for 5.5 hours at 55°C. Stop stirring and age for 24 hours while keeping the temperature constant. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0175] (6): The environmentally friendly microcapsule matrix obtained in step (5) was added to a Tris buffer solution with a pH of 8.5. The mass ratio of the Tris buffer solution to the deodorizing environmentally friendly microcapsule matrix was 60:1. Then, dopamine hydrochloride was added to make the concentration of dopamine in the reaction system 6 mg / mL. The mixture was stirred at 200 rpm for 12 hours at 25°C. The stirring was then stopped. The bottom solid powder was filtered and washed, and then vacuum dried at -30°C for 5 hours.

[0176] (7): Mix 1 part by weight of anhydrous copper sulfate and 50 parts by weight of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by weight of the solid particles obtained after drying in step (6) and the copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 hour at 110°C.

[0177] (8): Add 3.5 parts by weight of potassium sulfite to 50 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 60 °C. Add the resulting mixed solution to the reaction vessel (7), close the lid, and stir at 200 rpm for 4 h at 90 °C. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30 °C for 5 h to obtain environmentally friendly microcapsules with a particle size of 3.07~7.81 μm.

[0178] b: Preparation of environmentally friendly asphalt:

[0179] I: Mix 2 parts by weight of 4-maleiminophenol, 6-tert-butyl-m-cresol, tris(nonylphenol) phosphite and p-(dipropylamino)benzaldehyde in equal proportions, and then disperse them in 6 parts by weight of furfural refined oil. Further add 0.5 parts by weight of 3-methacryloyloxypropyltrimethoxysilane and 0.5 parts by weight of erucamide, and stir and mix at 50°C and 400 rpm for 2 hours.

[0180] II: 4.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 200,000, 3.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 23 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 140°C for 1.5 h and an extrusion temperature of 140°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 71 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0182] c: Mix 0.3 parts by weight of the environmentally friendly 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 94.7 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 4

[0184] a: Preparation of environmentally friendly microcapsules:

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

[0186] S1: Weigh 10.3 parts by weight of n-propyl titanate and 8 parts by weight of n-butanol and add them to a flask. Stir for 2 hours at 45°C and 450 rpm to obtain a titanium precursor solution.

[0187] S2: Slowly add 10wt% ammonia water to the S1 solution until the pH of the reaction system is 10.5, and continue stirring at 450 rpm for 2 hours at 45℃ to obtain titanium precursor sol.

[0188] S3: Add 9.2 parts by weight of Ba(OH)2·8H2O and 18 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 85°C.

[0189] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 145℃, stir at 400 rpm for 25 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.

[0190] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by weight of hexadecyltrimethylammonium bromide to 40 parts by weight of formamide. Modify by stirring at 200 rpm for 4 hours at 150°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 40-60 nm).

[0191] (2): Mix jasmine aldehyde, linalool, ethyl hexanoate and limonene in equal weight ratios, and stir at 400 rpm for 10 minutes at 50°C to obtain core material mixture.

[0192] (3): 4.5 parts by weight of the core material mixture obtained in step (2), 1.8 parts by weight of the barium titanate nanoparticles obtained in step (1) and 35 parts by weight of dimethylacetamide were stirred at 350 rpm for 4.5 hours at 55°C.

[0193] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 9:5. Continue stirring at 400 rpm for 5 hours at 55°C to obtain Pickering emulsion.

[0194] (5): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (4) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 400 rpm for 5.5 hours at 55°C. Stop stirring and age for 24 hours while keeping the temperature constant. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0195] (6): The environmentally friendly microcapsule matrix obtained in step (5) was added to a Tris buffer solution with a pH of 8.5. The mass ratio of the Tris buffer solution to the deodorizing environmentally friendly microcapsule matrix was 60:1. Then, dopamine hydrochloride was added to make the concentration of dopamine in the reaction system 6 mg / mL. The mixture was stirred at 200 rpm for 12 hours at 25°C. The stirring was then stopped. The bottom solid powder was filtered and washed, and then vacuum dried at -30°C for 5 hours.

[0196] (7): Mix 1 part by weight of anhydrous copper sulfate and 50 parts by weight of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by weight of the solid particles obtained after drying in step (6) and the copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 hour at 110°C.

[0197] (8): Add 3.5 parts by weight of potassium sulfite to 50 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 60 °C. Add the resulting mixed solution to the reaction vessel (7), close the lid, and stir at 200 rpm for 4 h at 90 °C. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30 °C for 5 h to obtain environmentally friendly microcapsules with a particle size of 3.07~7.81 μm.

[0198] b: Preparation of environmentally friendly asphalt:

[0199] I: Mix N-(4-aminophenyl)maleimide, 2-tert-butyl-p-cresol, tris(2-cyclohexylphenyl)phosphite, and 4-(diethylamino)salicylaldehyde in equal proportions, and disperse them in 5 parts by weight of catalytic cracking slurry. Then add 0.5 parts by weight of 3-aminopropyltriethoxysilane and 0.5 parts by weight of oleamide, and stir and mix at 50°C and 400 rpm for 2 hours.

[0200] II: 3.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 200,000, 2.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 23 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 140°C for 1.5 h and an extrusion temperature of 140°C to obtain asphalt additive;

[0201] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 71 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0202] c: Mix 0.3 parts by weight of the environmentally friendly 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 94.7 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.

[0203] Example 5

[0204] a: Preparation of environmentally friendly microcapsules:

[0205] (1): Preparation of barium titanate nanoparticles:

[0206] S1: Weigh 14.5 parts by weight of n-propyl titanate and 12 parts by weight of n-butanol and add them to a flask. Stir for 1.5 hours at 45°C and 400 rpm to obtain a titanium precursor solution.

[0207] 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 1.5 hours at 45℃ to obtain titanium precursor sol;

[0208] S3: Add 13 parts by weight of Ba(OH)2·8H2O and 13 parts by weight of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 90°C.

[0209] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 150℃, stir at 500 rpm for 23 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.

[0210] S5: Add 1 part by weight of the primary barium titanate nanoparticles obtained in step S4 and 6 parts by weight of octadecyltrimethylammonium chloride to 20 parts by weight of formamide. Modify by stirring at 200 rpm for 7 hours at 150°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 40-60 nm).

[0211] (2): Mix jasmine aldehyde, linalool, ethyl hexanoate and limonene in equal weight ratios, and stir at 400 rpm for 10 minutes at 50°C to obtain core material mixture.

[0212] (3): 4.5 parts by weight of the core material mixture obtained in step (2), 1.8 parts by weight of the barium titanate nanoparticles obtained in step (1) and 35 parts by weight of dimethylacetamide were stirred at 350 rpm for 4.5 hours at 55°C.

[0213] (4): Add methyl silicate to the reaction system of step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 9:5. Continue stirring at 400 rpm for 5 hours at 55°C to obtain Pickering emulsion.

[0214] (5): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (4) using a peristaltic pump until the pH of the reaction system is 4.5. Continue stirring at 400 rpm for 5.5 hours at 55°C. Stop stirring and age for 24 hours while keeping the temperature constant. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0215] (6): The environmentally friendly microcapsule matrix obtained in step (5) was added to a Tris buffer solution with a pH of 8.5. The mass ratio of the Tris buffer solution to the deodorizing environmentally friendly microcapsule matrix was 60:1. Then, dopamine hydrochloride was added to make the concentration of dopamine in the reaction system 4.8 mg / mL. The mixture was stirred at 200 rpm for 12 hours at 25°C. The stirring was then stopped. The bottom solid powder was filtered and washed, and then vacuum dried at -30°C for 5 hours.

[0216] (7): 0.5 parts by weight of anhydrous copper sulfate and 80 parts by weight of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by weight of the solid particles obtained after drying in step (6) and the copper sulfate solution were added to the reactor. The reactor lid was closed and the mixture was stirred at 200 rpm for 1 h at 120°C.

[0217] (8): Add 2 parts by weight of potassium sulfite to 35 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 60 °C. Add the resulting mixed solution to the reaction vessel (7), close the lid, and stir at 200 rpm for 4 h at 90 °C. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30 °C for 5 h to obtain environmentally friendly microcapsules with a particle size of 2.80~7.13 μm.

[0218] b: Preparation of environmentally friendly asphalt:

[0219] I: Two parts by weight of N-phenylmaleimide, 2-tert-butyl-p-cresol, tris(2-cyclohexylphenyl) phosphite, and 4-diethylaminobenzaldehyde were mixed in equal proportions and dispersed in five parts by weight of extracted oil. Then, 0.5 parts by weight of 3-aminopropyltriethoxysilane and 0.5 parts by weight of oleamide were added, and the mixture was stirred at 400 rpm for 2 hours at 50°C.

[0220] II: 4.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 200,000, 3.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 23 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 140°C for 1.5 h and an extrusion temperature of 140°C to obtain asphalt additive;

[0221] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 71 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0222] c: Mix 0.23 parts by weight of the environmentally friendly 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 94.7 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.

[0223] Comparative Example 1

[0224] Five parts by weight of molten base asphalt at 150℃ (penetration 71 1 / 10 mm 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.

[0225] Comparative Example 2

[0226] a: Preparation of environmentally friendly microcapsules:

[0227] (1): Mix jasmine aldehyde, linalool, ethyl hexanoate and limonene in equal weight ratios, and stir at 400 rpm for 10 minutes at 50°C to obtain core material mixture.

[0228] (2): 4.5 parts by weight of the core material mixture obtained in step (1), 1.8 parts by weight of hexadecyltrimethylammonium bromide and 35 parts by weight of dimethylacetamide were stirred at 350 rpm for 4.5 hours at 55°C.

[0229] (3): Add methyl silicate to the reaction system of step (2), the mass ratio of core material mixture to tetraethyl orthosilicate is 9:5, and continue to stir at 400 rpm for 5 hours at 55°C to obtain Pickering emulsion.

[0230] (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 400 rpm for 5.5 hours at 55°C. Stop stirring and age for 24 hours while keeping the temperature constant. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0231] (5): The environmentally friendly microcapsule matrix obtained in step (4) is added to a Tris buffer solution with a pH of 8.5. The mass ratio of the Tris buffer solution to the deodorizing environmentally friendly microcapsule matrix is ​​60:1. Then, dopamine hydrochloride is added to make the concentration of dopamine in the reaction system 6 mg / mL. The mixture is stirred at 200 rpm for 12 hours at 25°C. The stirring is then stopped. The bottom solid powder is filtered and washed, and then vacuum dried at -30°C for 5 hours.

[0232] (6): Mix 1 part by weight of anhydrous copper sulfate and 50 parts by weight of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by weight of the solid particles obtained after drying in step (5) and the copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 h at a temperature of 110°C.

[0233] (7): Add 3.5 parts by weight of potassium sulfite to 50 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 60 °C. Add the resulting mixed solution to the reaction vessel (6), close the lid, and stir at 200 rpm for 4 h at 90 °C. Finally, filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h to obtain environmentally friendly microcapsules.

[0234] b: Preparation of environmentally friendly asphalt:

[0235] I: Mix N-(4-aminophenyl)maleimide, 2-tert-butyl-p-cresol, tris(2-cyclohexylphenyl)phosphite, and 4-(diethylamino)salicylaldehyde in equal proportions, and disperse them in 5 parts by weight of catalytic cracking slurry. Then add 0.5 parts by weight of 3-aminopropyltriethoxysilane and 0.5 parts by weight of oleamide, and stir and mix at 50°C and 400 rpm for 2 hours.

[0236] II: 4.5 parts by mass of styrene-butadiene-styrene copolymer with a relative molecular mass of 200,000, 3.5 parts by mass of ethylene-vinyl acetate copolymer with a combined vinyl acetate content of 23 wt%, and the mixture obtained in step I are kneaded in a preheated kneader at a kneading temperature of 140°C for 1.5 h and an extrusion temperature of 140°C to obtain asphalt additive;

[0237] III: Mix 100 parts by weight of base asphalt at 143°C in a molten state (25°C penetration 71 1 / 10 mm) with asphalt additive at 500 rpm for 2 hours to obtain environmentally friendly asphalt.

[0238] c: Mix 0.3 parts by weight of the environmentally friendly 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 94.7 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.

[0239] Test Example 1

[0240] Sulfides and benzene compounds are the main causes of the irritating odor in asphalt mixture fumes. Asphalt mixture samples prepared in Examples 1-6 and Comparative Examples 1-2 were stored at 160°C for 5 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, where fume enrichment was carried out at 150°C for 8 hours. After enrichment, the gas in the sealed container was extracted and tested. The data obtained are shown in Table 1 below.

[0241] Table 1

[0242]

[0243]

[0244] Test Example 2

[0245] 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.

[0246] Table 2

[0247] Test sample Mixture loss rate, % Example 1 4.64 Example 2 4.77 Example 3 4.82 Example 4 8.15 Example 5 6.55 Comparative Example 1 25.82 Comparative Example 2 13.55

[0248] 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 environmentally friendly asphalt mixture, comprising the following components by weight: Environmentally friendly asphalt: 4-6 parts; Environmentally friendly microcapsules: 0.1-1 part, preferably 0.3-0.8 parts; Graded stone: 93-95.9 parts per unit area; The environmentally friendly microcapsule comprises a composite shell and a core material. The composite shell includes an inorganic base shell, barium titanate nanoparticles, polydopamine, and cuprous oxide. The core material includes a neutralizing agent.

2. The environmentally friendly asphalt mixture according to claim 1, characterized in that, The environmentally friendly microcapsules have a particle size of 1-10 μm; And / or, the mass ratio of the composite shell material to the core material is 1:(0.2-2); And / or, the deodorizing agent is one or more of aldehydes, alcohols, esters, and alkenes, preferably including aldehydes, alcohols, esters, and alkenes simultaneously; 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, polydopamine, and cuprous oxide is 1:(0.2-0.8):(0.1-0.5):(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.

3. The environmentally friendly 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; Amide compounds: 0.1-10 parts; Styrene-butadiene-styrene polymer: 1-20 parts, preferably 4-8 parts; Ethylene-vinyl acetate copolymer: 1-20 parts, preferably 3-7 parts; Base bitumen: 50-500 parts.

4. The environmentally friendly asphalt mixture according to claim 3, characterized in that, 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. 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-glycidyl etheroxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane; And / or, the amide compound is selected from higher fatty acid amides having more than 18 carbon atoms, preferably selected from one or more of oleamide, erucamide, oleyl palmitamide, and docosamide; 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.

5. The method for preparing the environmentally friendly asphalt mixture according to any one of claims 1-4, comprising: a: Preparation of environmentally friendly microcapsules; b: Prepare environmentally friendly asphalt and heat it to melt; c: Mix the environmentally friendly microcapsules obtained in step a, the environmentally friendly asphalt in the molten state of step b, and the graded aggregate to obtain an asphalt mixture.

6. The method according to claim 4, characterized in that, Step a, the method for preparing environmentally friendly microcapsules, includes: (1) Preparation of barium titanate nanoparticles; (2) Stir and mix one or more deodorizing agents to obtain a core material mixture; (3) The core material mixture and barium titanate nanoparticles are stirred and mixed in a solvent; (4) Add the inorganic base shell precursor to the reaction system of step (3), stir and mix to obtain Pickering emulsion; (5) Adjust the pH value of the Pickering emulsion obtained in step (4), continue stirring, then age, filter, freeze dry, and obtain an environmentally friendly microcapsule matrix; (6) Disperse the environmentally friendly microcapsule matrix obtained in step (5) in a buffer solution, add dopamine hydrochloride, process with stirring, then filter, wash, freeze dry to obtain solid particles; (7) Add the solid particles and copper ion solution obtained in step (6) into the reaction vessel and carry out the reaction with stirring; (8) Mix the reducing agent with the buffer solution, stir to dissolve, and then add it to the reaction system of step (7). Stir to carry out the reaction, then filter, wash, freeze dry, and obtain environmentally friendly microcapsules.

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 5, characterized in that, In step (3), 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 (3), the mass ratio of the solvent to the barium titanate nanoparticles is (10-40):1; And / or, in step (3), the stirring speed is 400-600 rpm, the stirring temperature is 30-60℃, and the stirring time is 4-6 hours.

14. The method according to claim 6, characterized in that, In step (4), the inorganic base shell precursor is at least one of silicate ester compounds and titanate compounds, preferably a silicate ester compound; the silicate ester compound is at least one of methyl silicate, tetraethyl orthosilicate, tetraethyl orthosilicate, and tetrabutyl orthosilicate. And / or, in step (4), the stirring speed is 400-600 rpm, the stirring temperature is 30-60℃, and the stirring time is 4-6 hours.

15. The method according to claim 6, characterized in that, In step (5), the pH is adjusted to 3-6; the stirring speed is 400-600 rpm, the stirring temperature is 30-60℃, and the stirring time is 4-6 hours. And / or, in step (5), the aging conditions are: standing at 40-60°C for 12-30 hours; the freeze-drying conditions are: vacuum drying at -40-20°C for 4-8 hours.

16. The method according to claim 6, characterized in that, In step (6), the buffer solution is at least one of phosphate buffer, carbonate buffer, and tris(hydroxymethyl)aminomethane hydrochloride buffer. And / or, in step (6), the pH value of the buffer solution is 8-10; And / or, in step (6), the mass ratio of the buffer solution to the environmentally friendly microcapsule matrix obtained in step (5) is (10-100):1; And / or, in step (6), after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL; And / or, in step (6), the stirring speed is 100-300 rpm, the stirring temperature is 20-40°C, and the stirring time is 12-24 hours; And / or, in step (6), 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 6, characterized in that, In step (7), the copper ion solution has a copper ion concentration of 0.05-0.5 mol / L; And / or, in step (7), the mass ratio of the solid particles and copper ion solution obtained in step (6) is 1:(50-200); And / or, in step (7), 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 (8), the reducing agent is a sulfite reducing agent, preferably selected from at least one of potassium sulfite and sodium sulfite; And / or, in step (8), the buffer solution is selected from at least one of acetate buffer and phosphate buffer, preferably acetate buffer; the pH value of the buffer solution is 4.5-6.5; And / or, in step (8), the mass ratio of the reducing agent to the buffer solution is 1:(10-20); And / or, in step (8), when stirring to dissolve, the stirring speed is 200-450 rpm, the stirring temperature is 40-80°C, and the stirring time is 1-5 hours; And / or, in step (8), when the reaction is carried out under stirring, the stirring speed is 100-450 rpm, the reaction temperature is 60-95°C, and the reaction time is 2-5 hours; And / or, in step (8), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

19. The method according to claim 5, characterized in that, Step b, the method for preparing environmentally friendly asphalt, includes: I: Heat and stir to mix the odor-neutralizing active ingredient, silane coupling agent, dispersant, and amide 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: After mixing the asphalt additive obtained in step II with the molten base asphalt, an environmentally friendly asphalt is obtained.

20. 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-5min.

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