Environment-friendly microcapsule, preparation method and application thereof

Abstract

The application discloses an environment-friendly microcapsule and a preparation method and application thereof. The environment-friendly microcapsule comprises a composite shell material and a core material, the composite shell material comprises an inorganic base shell, barium titanate nanoparticles, polydopamine and cuprous oxide, and the core material comprises a deodorant. The environment-friendly microcapsule can not only efficiently and durably reduce the content of irritating gas in flue gas, but also can emit a pleasant fragrance during construction, thereby providing a new idea for building material environmental protection application.

Description

Technical Field

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

[0002] Currently, countries worldwide, including China, are facing increasingly severe environmental challenges. The accelerated pace of urbanization has led to the continuous expansion of urban road networks, the core of urban infrastructure. Traditional asphalt pavements, with their excellent load-bearing and traffic capacity, meet the basic needs of modern transportation; however, the asphalt fumes produced during their manufacturing process cannot be ignored. These fumes are rich in various harmful substances and are highly irritating, not only contradicting environmental protection principles but also hindering sustainable economic development and posing a potential threat to human health.

[0003] Currently, additive modification technology is the mainstream method for reducing asphalt fume emissions. Its core lies in utilizing highly reactive compounds as additives. These additives can chemically react with the volatile components in asphalt, enhancing the stability and durability of asphalt molecules, thereby reducing the release of harmful gases in high-temperature construction environments. However, this technology also has some limitations in practical applications. First, because additives need to be added when the asphalt temperature is high to ensure thorough mixing, their low boiling point often leads to premature volatilization of some additives, failing to fully exert their intended effect and affecting the fume emission reduction performance. Second, research shows that the stability of the products generated from the reaction between additives and asphalt under high-temperature storage conditions needs improvement; they are prone to decomposition after long-term storage, thus weakening the fume emission reduction performance of asphalt.

[0004] CN117777742A discloses a odor-neutralizing asphalt modifier, its preparation method, and its application. This method directly adds the odor-neutralizing active component to high-temperature asphalt, which leads to a significant reduction in the activity effect of the odor-neutralizing component, making it unsuitable for long-term transportation and storage.

[0005] Therefore, future research should focus on developing new additives that possess higher thermal stability and reactivity, can function effectively over a wider temperature range, and whose compounds with asphalt have a longer shelf life. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides an environmentally friendly microcapsule, its preparation method, and its application. The environmentally friendly microcapsule of this invention can not only efficiently and persistently reduce the content of irritating gases in flue gas, but also emit a pleasant aroma during construction, providing a completely new approach to the environmentally friendly application of building materials.

[0007] The first aspect of the present invention provides an environmentally friendly microcapsule, the environmentally friendly microcapsule comprising a composite shell material and a core material, the composite shell material comprising an inorganic base shell, barium titanate nanoparticles, polydopamine and cuprous oxide, and the core material comprising a deodorizing agent.

[0008] Furthermore, the particle size of the environmentally friendly microcapsules is 1-10 μm.

[0009] Furthermore, the mass ratio of the composite shell material to the core material is 1:(0.2-2).

[0010] 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).

[0011] Furthermore, the inorganic base shell is made of at least one material selected from silicon dioxide and titanium dioxide, preferably silicon dioxide.

[0012] Furthermore, the odor neutralizer is one or more of aldehydes, alcohols, esters, and alkenes, preferably including aldehydes, alcohols, esters, and alkenes simultaneously.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] Further, the alkene is selected from cyclic terpenes with a molecular weight greater than 130. It is further selected from one or more of limonene, α-terpinene, α-phellandrene, α-pinene, thujone, juniperene, and longleafene.

[0017] A second aspect of the present invention provides a method for preparing the above-mentioned environmentally friendly microcapsules, comprising:

[0018] (1) Preparation of barium titanate nanoparticles;

[0019] (2) Stir and mix one or more deodorizing agents to obtain a core material mixture;

[0020] (3) The core material mixture and barium titanate nanoparticles are stirred and mixed in a solvent;

[0021] (4) Add the inorganic base shell precursor to the reaction system of step (3), stir and mix to obtain Pickering emulsion;

[0022] (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;

[0023] (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;

[0024] (7) Add the solid particles and copper ion solution obtained in step (6) into the reaction vessel and carry out the reaction with stirring;

[0025] (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.

[0026] Furthermore, the method for preparing barium titanate nanoparticles in step (1) includes:

[0027] S1: Stir and mix the titanium precursor and solvent;

[0028] S2: Adjust the pH of the mixed solution obtained in S1 and stir until a titanium precursor sol is obtained;

[0029] S3: Mix the barium precursor with water;

[0030] 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.

[0031] 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.

[0032] Further, in step S1, the titanium precursor is selected from at least one of tetraethyl titanate, n-propyl titanate, and tetrabutyl titanate.

[0033] 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.

[0034] 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.

[0035] Further, in step S1, the mass ratio of the titanium precursor to the solvent is (1-20):1.

[0036] Further, in step S2, the pH of the mixed solution from S1 is adjusted to pH = 9-12.

[0037] 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.

[0038] 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.

[0039] Further, in step S3, the barium precursor is at least one of Ba(OH)2, Ba(OH)2·H2O, and Ba(OH)2·8H2O.

[0040] 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.

[0041] 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.

[0042] 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).

[0043] 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.

[0044] Furthermore, in step S4, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0045] Furthermore, in step S4, the grinding specifically means grinding until there are no obvious lumps.

[0046] Furthermore, in step S5, the diameter of the barium titanate nanoparticles is 20-100 nm.

[0047] Further, in step S5, the surfactant is a cationic surfactant, preferably at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] Furthermore, in step S5, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0052] 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.

[0053] 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.

[0054] Further, in step (3), the mass ratio of the solvent to the barium titanate nanoparticles is (10-40):1.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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---20℃ for 4-8 hours.

[0060] 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).

[0061] Furthermore, in step (6), the pH value of the buffer solution is preferably 8-10.

[0062] 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.

[0063] Furthermore, in step (6), after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

[0064] 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.

[0065] Furthermore, in step (6), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0066] 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.

[0067] Further, in step (7), the concentration of copper ions in the copper ion solution is 0.05-0.5 mol / L.

[0068] Further, in step (7), the mass ratio of the solid particles and copper ion solution obtained in step (6) is 1:(50-200).

[0069] 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.

[0070] Further, in step (8), the reducing agent is a sulfite reducing agent, preferably selected from at least one of potassium sulfite and sodium sulfite.

[0071] 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.

[0072] Further, in step (8), the mass ratio of the reducing agent to the buffer solution is 1:(10-20).

[0073] 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.

[0074] 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.

[0075] Further, in step (8), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0076] A third aspect of the present invention provides an application of the above-mentioned environmentally friendly microcapsules in environmentally friendly asphalt.

[0077] Furthermore, the environmentally friendly asphalt, by weight, comprises the following components:

[0078] Base bitumen, 50-500 parts;

[0079] The above-mentioned environmentally friendly microcapsules are used in quantities of 0.1-5 parts, preferably 1-5 parts.

[0080] Furthermore, the penetration of the base asphalt at 25°C is 30-210 1 / 10 mm.

[0081] Further, the base asphalt is heated to 133-153℃, and the environmentally friendly microcapsules are added at a speed of 200-400 rpm. After stirring for 2-4 hours, the odor-free and environmentally friendly asphalt can be obtained.

[0082] Compared with the prior art, the present invention has the following advantages:

[0083] (1) 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.

[0084] (2) The environmentally friendly microcapsule of the present invention comprises 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. The second function is that after being synthesized by the method described in the present invention, cuprous oxide will form a porous structure with a large specific surface area on the surface of the microcapsule, which effectively improves the adsorption capacity of cuprous oxide for 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 improving the smoke-suppressing ability of the environmentally friendly microcapsule.

[0085] (3) The environmentally friendly microcapsules of the present invention encapsulate the low-boiling-point odor-neutralizing active components in the composite shell material. These active components can be slowly released from the microcapsules during the storage and construction of asphalt, avoiding the problems of reduced emission reduction effect and short duration caused by the active components not reacting with the relevant components in the asphalt due to high temperature volatilization. Detailed Implementation

[0086] To further illustrate the technical solution of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0087] The non-methane total hydrocarbons in the asphalt flue gas described in this invention are tested using a portable total hydrocarbon analyzer in accordance with the technical requirements and detection methods for portable monitoring instruments for total hydrocarbons, methane and non-methane total hydrocarbons in ambient air and exhaust gas, as specified in HJ 1012-2018.

[0088] The sulfides in the asphalt flue gas described in this invention are tested by gas chromatography according to the standard GB / T 14678-1993, "Determination of hydrogen sulfide, methanethiol, dimethyl sulfide and dimethyl disulfide in air quality".

[0089] 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.

[0090] Example 1

[0091] (1): Preparation of barium titanate nanoparticles

[0092] S1: Weigh 18 parts by mass of tetrapropyl titanate and 12 parts by mass of methanol and add them to a flask. Stir at 30°C and 450 rpm for 1 hour to obtain a titanium precursor solution.

[0093] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 9, and continue stirring at 400 rpm for 1 hour at 30℃ to obtain titanium precursor sol.

[0094] S3: Add 9 parts by mass of Ba(OH)2 and 9 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 90°C.

[0095] 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 28 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.

[0096] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 3 parts by mass of hexadecyltrimethylammonium bromide to 30 parts by mass of formamide. Modify by stirring at 200 rpm for 4 hours at 130°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).

[0097] (2): After mixing cinnamaldehyde, geraniol, benzyl salicylate and limonene in equal weight proportions, the mixture was stirred at 400 rpm for 10 minutes at 50°C to obtain the core material mixture.

[0098] (3): 2 parts by weight of the core material mixture obtained in step (2), 1 part by weight of the barium titanate nanoparticles obtained in step (1) and 20 parts by weight of N,N-dimethylformamide were stirred at 400 rpm for 5 hours at 50°C.

[0099] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0100] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0101] (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 5 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.

[0102] (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.

[0103] (8): Add 3 parts by weight of sodium sulfite to 30 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 50 °C; add the resulting mixed solution to the reaction vessel (7), close the vessel 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 2.18~5.53 μm.

[0104] Add 1 part by weight of the environmentally friendly microcapsules obtained in step (8) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0105] Example 2

[0106] (1): Preparation of barium titanate nanoparticles

[0107] S1: Weigh 14 parts by mass of tetrapropyl titanate and 10 parts by mass of ethylene glycol and add them to a flask. Stir at 45°C and 450 rpm for 1 hour to obtain a titanium precursor solution.

[0108] 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 45℃ to obtain the titanium precursor sol.

[0109] S3: Add 6.7 parts by mass of Ba(OH)2 and 8 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 90°C.

[0110] 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 26 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.

[0111] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 4 parts by mass of dodecyl dimethyl benzyl ammonium chloride to 45 parts by mass 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 40-60 nm).

[0112] (2): Mix jasmine aldehyde, borneol, isoamyl salicylate, and α-pinene in equal weight ratios, and stir at 400 rpm for 10 minutes at 50°C to obtain a core material mixture.

[0113] (3): 2 parts by weight of the core material mixture obtained in step (2), 1 part by weight of the barium titanate nanoparticles obtained in step (1) and 20 parts by weight of formamide are stirred at 400 rpm for 5 hours at 50°C.

[0114] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0115] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0116] (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 5 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.

[0117] (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.

[0118] (8): Add 3 parts by weight of sodium sulfite to 30 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 50 °C; add the resulting mixed solution to the reaction vessel (7), close the vessel 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 2.18~5.53 μm.

[0119] Add 1 part by weight of the environmentally friendly microcapsules obtained in step (8) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0120] Example 3

[0121] (1): Preparation of barium titanate nanoparticles

[0122] S1: Weigh 16 parts by mass of tetrapropyl titanate and 14 parts by mass of butanediol and add them to a flask. Stir at 40°C and 450 rpm for 1 hour to obtain a titanium precursor solution.

[0123] 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 40℃ to obtain titanium precursor sol.

[0124] S3: Add 7.8 parts by mass of Ba(OH)2 and 10 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 90°C.

[0125] 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 27 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.

[0126] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 6 parts by mass of hexadecyltrimethylammonium bromide to 40 parts by mass of formamide. Modify by stirring at 200 rpm for 4 hours at 130°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).

[0127] (2): Mix methylamyl cinnamaldehyde and α-terpineol in equal weight ratios, and stir at 400 rpm for 10 minutes at 50°C to obtain a core material mixture.

[0128] (3): 1.8 parts by weight of the core material mixture obtained in step (2), 1 part by weight of the barium titanate nanoparticles obtained in step (1) and 20 parts by weight of N,N-dimethylformamide were stirred at 400 rpm for 5 hours at 50°C.

[0129] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0130] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0131] (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 5 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.

[0132] (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.

[0133] (8): Add 3 parts by weight of sodium sulfite to 30 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 50 °C; add the resulting mixed solution to the reaction vessel (7), close the vessel 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 2.14~5.41 μm.

[0134] Add 1 part by weight of the environmentally friendly microcapsules obtained in step (8) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0135] Example 4

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

[0137] S1: Weigh 9 parts by mass of tetrapropyl titanate and 7 parts by mass of methanol and add them to a flask. Stir at 35°C and 450 rpm for 1 hour to obtain a titanium precursor solution.

[0138] 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.

[0139] S3: Add 5 parts by mass of Ba(OH)2 and 5 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 90°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 28 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 mass of the primary barium titanate nanoparticles obtained in step S4 and 3 parts by mass of hexadecyltrimethylammonium bromide to 30 parts by mass of formamide. Modify by stirring at 200 rpm for 4 hours at 130°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).

[0142] (2): After mixing cinnamaldehyde, geraniol, benzyl salicylate and limonene in equal weight proportions, the mixture was stirred at 400 rpm for 10 minutes at 50°C to obtain the core material mixture.

[0143] (3): 2 parts by weight of the core material mixture obtained in step (2), 1 part by weight of the barium titanate nanoparticles obtained in step (1) and 20 parts by weight of N,N-dimethylformamide were stirred at 400 rpm for 5 hours at 50°C.

[0144] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:0.85. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0145] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0146] (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.

[0147] (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.

[0148] (8): Add 3 parts by weight of sodium sulfite to 30 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 50 °C; add the resulting mixed solution to the reaction vessel (7), close the vessel 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 2.15~5.43 μm.

[0149] Add 1 part by weight of the environmentally friendly microcapsules obtained in step (8) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0150] Example 5

[0151] (1): Preparation of barium titanate nanoparticles

[0152] S1: Weigh 11 parts by mass of tetrapropyl titanate and 8 parts by mass of anhydrous ethanol and add them to a flask. Stir at 55°C and 450 rpm for 1 hour to obtain a titanium precursor solution.

[0153] 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 1 hour at 55℃ to obtain titanium precursor sol.

[0154] S3: Add 5.3 parts by mass of Ba(OH)2 and 7 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 95°C.

[0155] 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 26 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.

[0156] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 3 parts by mass of hexadecyltrimethylammonium bromide to 30 parts by mass of formamide. Modify by stirring at 200 rpm for 4 hours at 130°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).

[0157] (2): After mixing cinnamaldehyde, geraniol, benzyl salicylate and limonene in equal weight proportions, the mixture was stirred at 400 rpm for 10 minutes at 50°C to obtain the core material mixture.

[0158] (3): 2 parts by weight of the core material mixture obtained in step (2), 0.8 parts by weight of the barium titanate nanoparticles obtained in step (1) and 20 parts by weight of N,N-dimethylformamide were stirred at 400 rpm for 5 hours at 50°C.

[0159] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0160] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0161] (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 5 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.

[0162] (7): 1.5 parts by weight of anhydrous copper sulfate and 50 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 hour at 110°C.

[0163] (8): Add 3 parts by weight of sodium sulfite to 30 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 50 °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 2.32~5.88 μm.

[0164] Add 1 part by weight of the environmentally friendly microcapsules obtained in step (8) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0165] Example 6

[0166] (1): Preparation of barium titanate nanoparticles

[0167] S1: Weigh 12.5 parts by weight of n-propyl titanate and 10 parts by weight of n-butanol and add them to the flask.

[0168] A titanium precursor solution was prepared by stirring at 50℃ and 450 rpm for 1 hour.

[0169] 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 1.5 hours at 50℃ to obtain titanium precursor sol;

[0170] S3: Add 6 parts by mass of Ba(OH)2 and 6 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 2.5 h at 95°C.

[0171] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 160℃, stir at 450 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.

[0172] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 8 parts by mass of octadecyltrimethylammonium chloride to 30 parts by mass of formamide. Modify by stirring at 200 rpm for 3 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).

[0173] (2): Citral, 3,7-dimethyl-octen-2-ol, isoamyl salicylate, and α-phellandrene were mixed in equal weight ratios and stirred at 400 rpm for 10 minutes at 50°C to obtain a core material mixture.

[0174] (3): 2 parts by weight of the core material mixture obtained in step (2), 1 part by weight of the barium titanate nanoparticles obtained in step (1) and 20 parts by weight of formamide are stirred at 400 rpm for 5 hours at 50°C.

[0175] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0176] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0177] (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 5 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.

[0178] (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.

[0179] (8): Add 3 parts by weight of sodium sulfite to 30 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 50 °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 2.18~5.53 μm.

[0180] Add 0.5 parts by weight of the environmentally friendly microcapsules obtained in step (8) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0181] Comparative Example 1

[0182] 100 parts of base asphalt were heated to 143℃ and stirred at 400 rpm for 4 hours to obtain a base asphalt control sample.

[0183] Comparative Example 2

[0184] (1): Preparation of barium titanate nanoparticles

[0185] S1: Weigh 18 parts by mass of tetrapropyl titanate and 12 parts by mass of methanol and add them to a flask. Stir at 30°C and 450 rpm for 1 hour to obtain a titanium precursor solution.

[0186] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 9, and continue stirring at 400 rpm for 1 hour at 30℃ to obtain titanium precursor sol.

[0187] S3: Add 9 parts by mass of Ba(OH)2 and 9 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 2 hours at 90°C.

[0188] 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 28 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.

[0189] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 3 parts by mass of hexadecyltrimethylammonium bromide to 30 parts by mass of formamide. Modify by stirring at 200 rpm for 4 hours at 130°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).

[0190] (2): After mixing cinnamaldehyde, geraniol, benzyl salicylate and limonene in equal weight proportions, the mixture was stirred at 400 rpm for 10 minutes at 50°C to obtain the core material mixture.

[0191] (3): 2 parts by weight of the core material mixture obtained in step (2), 1 part by weight of the barium titanate nanoparticles obtained in step (1) and 20 parts by weight of N,N-dimethylformamide were stirred at 400 rpm for 5 hours at 50°C.

[0192] (4): Add tetraethyl orthosilicate to the reaction system in step (3). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0193] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0194] (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 5 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.

[0195] Add 1 part by weight of the environmentally friendly microcapsules obtained in step (6) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0196] Comparative Example 3

[0197] (1): The core material mixture was prepared by mixing cinnamaldehyde, geraniol, benzyl salicylate and limonene in equal weight ratios and stirring at 400 rpm for 10 minutes at 50°C.

[0198] (2): 2 parts by weight of the core material mixture obtained in step (1), 1 part by weight of hexadecyltrimethylammonium bromide and 20 parts by weight of N,N-dimethylformamide were stirred at 400 rpm for 5 hours at 50°C.

[0199] (3): Add tetraethyl orthosilicate to the reaction system in step (2). The mass ratio of the core material mixture to tetraethyl orthosilicate is 1:1. Continue stirring at 400 rpm for 5 hours at 50°C to obtain Pickering emulsion.

[0200] (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. Continue stirring at 400 rpm for 5 hours at 50°C. Stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry it at -30°C for 5 hours to obtain an environmentally friendly microcapsule matrix.

[0201] (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 5 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.

[0202] (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.

[0203] (7): Add 3 parts by weight of sodium sulfite to 30 parts by weight of acetate buffer solution with pH=6, and stir at 200 rpm for 1 h at 50 °C; add the resulting mixed solution to the reaction vessel (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h to obtain environmentally friendly microcapsules.

[0204] Add 1 part by weight of the environmentally friendly microcapsules obtained in step (7) to 100 parts of base asphalt at 143°C (25°C penetration 87 1 / 10 mm), and stir at 400 rpm for 4 hours to obtain odor-free environmentally friendly asphalt.

[0205] Test case

[0206] Sulfides and hydrocarbons are harmful substances in asphalt fumes that have a significant impact on human health. The asphalt samples prepared in Examples 1-6 and Comparative Examples 1-3 were stored at 133°C for 3 days. After storage, an equal mass of the stored asphalt was transferred to an asphalt fume enrichment and collection device, where fume enrichment was carried out at 143°C for 6 hours. After enrichment, the gas in the sealed container was extracted and tested. The data obtained are shown in Table 1 below.

[0207] Table 1

[0208]

[0209]

[0210] 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 microcapsule, characterized in that, 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 microcapsule according to claim 1, characterized in that, The environmentally friendly microcapsules have a particle size of 1-10 μm.

3. The environmentally friendly microcapsule according to claim 1, characterized in that, The mass ratio of the composite shell material to the core material is 1:(0.2-2); And / or, the composite shell material comprises an inorganic base shell / barium titanate nanoparticles / polydopamine / cuprous oxide, wherein the mass ratio of the inorganic base shell to the barium titanate nanoparticles, 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.

4. The environmentally friendly microcapsule according to claim 1, characterized in that, The deodorizing agent is one or more of aldehydes, alcohols, esters, and alkenes, preferably including aldehydes, alcohols, esters, and alkenes simultaneously; And / or, the aldehydes are selected from one or more of 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. And / or, 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 sandalwood alcohol. And / or, 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 laurylate, 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. And / or, the alkene is selected from cyclic terpenes with a molecular weight greater than 130; further selected from one or more of limonene, α-terpinene, α-phellandrene, α-pinene, thujone, cypressene, and longleafene.

5. A method for preparing the environmentally friendly microcapsules according to any one of claims 1-4, comprising: (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.

6. The method according to claim 5, 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.

7. The method according to claim 6, 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.

8. The method according to claim 6, 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.

9. The method according to claim 6, 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.

10. The method according to claim 6, 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.

11. The method according to claim 6, 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.

12. The method according to claim 5, characterized in that, In step (2), the stirring speed is 400-600 rpm, the stirring temperature is 30-70℃, and the stirring time is 3-10 minutes.

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 5, 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 5, 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 5, 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 5, 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 5, 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 application of the environmentally friendly microcapsules according to any one of claims 1-4 or the environmentally friendly microcapsules prepared by the method according to any one of claims 5-18 in environmentally friendly asphalt.

20. The application according to claim 19, characterized in that, The environmentally friendly asphalt, by weight, comprises the following components: Base bitumen, 50-500 parts; The environmentally friendly microcapsules are used in quantities of 0.1-5 parts, preferably 1-5 parts.

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