A deodorant temperature-controlling microcapsule, a preparation method and application thereof

Abstract

The application discloses a kind of net taste temperature control microcapsules and its preparation method and application.The net taste temperature control microcapsules of the application include composite shell material and core material, wherein the composite shell material includes inorganic base layer shell, barium titanate nanoparticles, polydopamine and cuprous oxide, the core material includes n-alkane with phase transition temperature of 40-60 DEG C, and the composite shell material surface is loaded with active smoke suppression compound.By adding the net taste temperature control microcapsules to various asphalt building materials, the content of active gas generated by high temperature effect of various asphalt building materials is efficiently and durably reduced, the high temperature stability of various asphalt building materials is improved, and the service time of various asphalt building materials is prolonged by the temperature control effect and net taste effect of microcapsules.

Description

Technical Field

[0001] This invention belongs to the field of functional materials, specifically relating to a deodorizing and temperature-controlled microcapsule, its preparation method, and its application. Background Technology

[0002] Asphalt-based building materials, such as widely used waterproof membrane asphalt and road petroleum asphalt, face complex and severe environmental challenges throughout their entire life cycle—from raw material processing and production to storage, transportation, and final road application. Road petroleum asphalt, in particular, while its hot-mix, hot-laying construction method can efficiently complete road construction, releases large amounts of harmful and irritating fumes during this process. This not only puts enormous pressure on the environmental ecosystem but also poses a potential threat to human health.

[0003] Furthermore, asphalt materials have an extremely high heat absorption capacity. In hot summers or under direct sunlight, the road surface temperature rises rapidly. This not only softens the asphalt layer, increasing the risk of road surface defects such as rutting, sulking, and bleeding, and shortening the road's lifespan, but also accelerates the release of volatile organic compounds (VOCs). These VOCs are not only important precursors to smog and photochemical smog, further worsening air quality and impacting public health, but they also exacerbate the urban heat island effect, causing persistently high urban temperatures and affecting residents' quality of life.

[0004] To address these challenges, current technological research primarily focuses on adding specific admixtures to asphalt, such as phase change material microcapsules and neutralizing agents, to attempt to solve the aforementioned problems. The introduction of phase change material microcapsules aims to absorb and release heat through the phase change process of their core material, thereby alleviating the problem of asphalt heating up too quickly due to heat absorption. However, this method cannot address the series of problems caused by asphalt fumes. Neutralizing agents react chemically with the volatile light components in asphalt to generate large molecular compounds, thus reducing the generation of fumes during construction to some extent. However, the large molecular compounds generated by this method may volatilize again due to insufficient stability during thermal storage and construction, forming new pollutants.

[0005] CN116082851A discloses a method for preparing self-temperature regulating and self-healing modified asphalt, which uses microcapsules that can reduce the temperature of asphalt pavement. This method can avoid problems such as asphalt softening and rutting caused by high temperature conditions to a certain extent. However, this technology cannot effectively deal with the problem of flue gas generated by asphalt under high temperature.

[0006] In conclusion, it is essential to develop a technology that can address both the high-temperature defects of asphalt building materials and the problem of high-temperature flue gas from asphalt. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention provides an odor-neutralizing and temperature-controlled microcapsule, its preparation method, and its application. By adding the odor-neutralizing and temperature-controlled microcapsule to various asphalt building materials, the temperature-controlling and odor-neutralizing effects of the microcapsule can be utilized to efficiently and persistently reduce the content of irritating gases generated by high temperatures in various asphalt building materials, improve the high-temperature stability of various asphalt building materials, and extend the service life of various asphalt building materials. This provides a brand-new approach for the long-life and environmentally friendly utilization of asphalt building materials.

[0008] The first aspect of the present invention provides a deodorizing and temperature-controlled microcapsule, wherein the deodorizing and temperature-controlled microcapsule comprises a composite shell material and a core material, wherein the composite shell material comprises an inorganic base shell, barium titanate nanoparticles, polydopamine and cuprous oxide, the core material comprises n-alkanes with a phase transition temperature of 40-60°C, and the surface of the composite shell material is loaded with an active smoke-suppressing compound.

[0009] Furthermore, the particle size of the odor-neutralizing and temperature-controlled microcapsules is 1-12 μm.

[0010] Furthermore, the mass ratio of the composite shell material to the core material of the odor-neutralizing and temperature-controlled microcapsule is 1:(0.2-2).

[0011] Further, the composite shell material comprises an inorganic base shell / barium titanate nanoparticles / polydopamine / cuprous oxide, wherein the mass ratio of the inorganic base shell to the barium titanate nanoparticles is 1:(0.2-0.8), the mass ratio of the inorganic base shell to the polydopamine is 1:(0.1-0.5), and the mass ratio of the inorganic base shell to the cuprous oxide is 1:(0.5-2).

[0012] Furthermore, the inorganic base shell is made of at least one material selected from silicon dioxide and titanium dioxide, preferably silicon dioxide.

[0013] Furthermore, the n-alkane with a phase transition temperature of 40-60℃ is one or more of n-octadecane, n-eicosane, and n-docosahexadecane.

[0014] Furthermore, the loading of the active smoke-suppressing compound accounts for 0.1wt%-20wt% of the total mass of the odor-neutralizing and temperature-controlled microcapsules.

[0015] Furthermore, the active smoke-suppressing compound is selected from one or more aldehyde compounds with a molecular weight greater than 160 and / or ketone compounds with a molecular weight greater than 150.

[0016] Furthermore, the aldehyde compound with a molecular weight greater than 160 is selected from one or more of 2-methylundecaldehyde, 10-undecenaldehyde, neojasmine aldehyde, citronellol, and citronellol.

[0017] Furthermore, the ketone compound with a molecular weight greater than 150 is selected from one or more of methyl nonyl ketone, geranylacetone, farnesyl acetone, dihydrodamastone, menthone, and allyl ionone.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned odor-neutralizing and temperature-controlled microcapsules, comprising:

[0019] (1) Preparation of barium titanate nanoparticles;

[0020] (2) Heat the core material raw material to melt, and mix it with solvent and barium titanate nanoparticles obtained in step (1);

[0021] (3) Add the inorganic base shell precursor to the reaction system of step (2), stir and mix to obtain Pickering emulsion;

[0022] (4) Adjust the pH value of the Pickering emulsion, continue stirring, then age, filter, wash, and freeze dry;

[0023] (5) Add the solid material obtained in step (4) to the buffer solution, add dopamine hydrochloride, stir and process, then filter, wash and freeze dry;

[0024] (6) Add the solid particles and copper ion solution obtained in step (5) into the reaction vessel and carry out the reaction with stirring;

[0025] (7) Mix the reducing agent with the buffer solution, stir to dissolve, and then add it to the reaction system of step (6). Stir to carry out the reaction, then filter, wash, and freeze dry.

[0026] (8) Mix the solid particles obtained in step (7) with water, adjust the pH, and then heat and stir; then add silane coupling agent, continue to react under stirring, and then filter, wash and freeze dry.

[0027] (9) The solid material obtained in step (8), the active smoke-suppressing compound, and the strong alkali are added to an organic solvent to react. After cooling, filtering, washing, and freeze-drying, the odor-neutralizing temperature-controlled microcapsules are obtained.

[0028] Furthermore, the method for preparing barium titanate nanoparticles in step (1) includes:

[0029] S1: Stir and mix the titanium precursor and solvent;

[0030] S2: Adjust the pH of the mixed solution obtained in S1 and stir until a titanium precursor sol is obtained;

[0031] S3: Mix the barium precursor with water;

[0032] 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.

[0033] 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.

[0034] Further, in step S1, the titanium precursor is selected from at least one of tetraethyl titanate, n-propyl titanate, and tetrabutyl titanate.

[0035] 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 anhydrous ethanol.

[0036] 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.

[0037] Further, in step S1, the mass ratio of the titanium precursor to the solvent is (1-20):1.

[0038] Further, in step S2, the pH of the mixed solution from S1 is adjusted to pH = 9-12.

[0039] 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.

[0040] 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.

[0041] Further, in step S3, the barium precursor is at least one of Ba(OH)2, Ba(OH)2·H2O, and Ba(OH)2·8H2O.

[0042] 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.

[0043] 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.

[0044] 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).

[0045] 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.

[0046] Furthermore, in step S4, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0047] Furthermore, in step S4, the grinding specifically means grinding until there are no obvious lumps.

[0048] Furthermore, in step S5, the diameter of the barium titanate nanoparticles is 20-100 nm.

[0049] Further, in step S5, the surfactant is a cationic surfactant, preferably at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride, and more preferably hexadecyltrimethylammonium bromide.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] Furthermore, in step S5, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0054] Furthermore, in step (2), the core material raw material is heated to a melting temperature of 40-80℃.

[0055] Further, in step (2), the solvent is an aprotic solvent with a boiling point >100℃, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0056] Further, in step (2), the mass ratio of the solvent to the barium titanate nanoparticles is (20-80):1.

[0057] Furthermore, in step (2), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

[0058] Further, in step (3), the inorganic base shell precursor is at least one of silicate ester compounds and titanate ester compounds, preferably a silicate ester compound; the silicate ester compound is preferably at least one of methyl silicate, tetraethyl orthosilicate, tetraethyl orthosilicate, and tetraethyl orthosilicate, more preferably tetraethyl orthosilicate.

[0059] Furthermore, in step (3), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

[0060] Further, in step (4), the pH value is adjusted to 3-6. The pH can be adjusted using a dilute acid, such as dilute hydrochloric acid.

[0061] Furthermore, in step (4), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

[0062] Further, in step (4), the aging conditions are: standing at 40-80℃ for 12-30 hours. The freeze-drying conditions are: vacuum drying at -40---20℃ for 4-8 hours.

[0063] Further, in step (5), the buffer solution is one or more of phosphate buffer, carbonate buffer, and tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer), preferably tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer).

[0064] Furthermore, in step (5), the pH value of the buffer solution is preferably 8-10.

[0065] Further, in step (5), the mass ratio of the buffer solution to the solid material obtained in step (4) is (10-100):1.

[0066] Furthermore, in step (5), after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

[0067] Furthermore, in step (5), the stirring speed is 100-300 rpm, the stirring temperature is 20-40℃, and the stirring time is 12-24 hours.

[0068] Furthermore, in step (5), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0069] Further, in step (6), the copper ion solution is prepared by mixing copper ion salt and deionized water, and the copper ion salt is preferably anhydrous copper sulfate.

[0070] Further, in step (6), the concentration of copper ions in the copper ion solution is 0.05-0.5 mol / L.

[0071] Further, in step (6), the mass ratio of the solid particles and copper ion solution obtained in step (5) is 1:(50-200).

[0072] Furthermore, in step (6), the stirring speed is 100-450 rpm, the reaction temperature is 100-190℃, and the reaction time is 1-5 hours.

[0073] Further, in step (7), the reducing agent is a sulfite reducing agent, preferably selected from at least one of potassium sulfite and sodium sulfite.

[0074] Further, in step (7), the buffer solution is selected from one of acetate buffer and phosphate buffer, preferably acetate buffer; the pH value of the buffer solution is 4.5-6.5.

[0075] Further, in step (7), the mass ratio of the reducing agent to the buffer solution is 1:(10-20).

[0076] Furthermore, in step (7), when stirring to dissolve, the stirring speed is 200-450 rpm, the stirring temperature is 40-80℃, and the stirring time is 1-5 hours.

[0077] Furthermore, in step (7), the stirring speed is 100-450 rpm, the reaction temperature is 60-95℃, and the reaction time is 2-5 hours.

[0078] Further, in step (7), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0079] Furthermore, in step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-6h.

[0080] Furthermore, in step (8), the pH is adjusted to 9-11. The pH can be adjusted using a conventional dilute alkaline solution, such as at least one of dilute sodium hydroxide solution or dilute potassium hydroxide solution.

[0081] Further, in step (8), the mass ratio of the solid particles obtained in step (7) to water is 1:(10-50).

[0082] Furthermore, in step (8), the added silane coupling agent is selected from one or more of chloropropyltriethoxysilane, chloromethyltriethoxysilane, dichloromethyltriethoxysilane, and chloromethyltriisopropoxysilane.

[0083] Further, in step (8), the mass ratio of the solid particles obtained in step (7) to the silane coupling agent is 1:(0.5-4).

[0084] Further, in step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-8h.

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

[0086] Further, in step (9), the organic solvent is selected from one or more of methanol, butanediol, ethylene glycol, n-butanol, and anhydrous ethanol, preferably anhydrous ethanol.

[0087] Further, in step (9), the mass ratio of the solid material obtained in step (8) to the organic solvent is 1:(20-80). The mass ratio of the solid material obtained in step (8) to the strong alkali is 1:(0.5-2).

[0088] Furthermore, in step (9), the strong alkali is either solid KOH or solid NaOH, preferably solid KOH.

[0089] Furthermore, in step (9), the reaction is carried out under reflux and the reaction conditions are: reaction temperature of 80-210℃ and reaction time of 5-10 hours.

[0090] Further, in step (9), the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0091] The third aspect of this invention provides an application of odor-neutralizing and temperature-controlled microcapsules in odor-neutralizing and temperature-controlled asphalt materials.

[0092] The odor-neutralizing and temperature-controlled asphalt material comprises the following components by weight:

[0093] The above-mentioned odor-neutralizing and temperature-controlled microcapsules: 0.1-10 parts, preferably 1.2-3 parts.

[0094] Base asphalt: 50-200 parts.

[0095] Furthermore, the penetration of the base asphalt at 25°C is 30-210 1 / 10 mm.

[0096] Furthermore, the preparation method of the odor-neutralizing and temperature-controlled asphalt material includes:

[0097] Add the odor-neutralizing and temperature-controlled microcapsules to the base asphalt that has been preheated to 133-153℃, and stir at 200-400 rpm for 2-4 hours to obtain the odor-neutralizing and temperature-controlled asphalt material.

[0098] Compared with the prior art, the present invention has the following advantages:

[0099] (1) The odor-neutralizing and temperature-controlled microcapsule of the present invention comprises an inorganic base shell, barium titanate nanoparticles, polydopamine and cuprous oxide, wherein the barium titanate nanoparticles have multiple functions. Firstly, during the preparation process, the modified barium titanate nanoparticles, due to their nanoscale size, can stably exist between the water and oil interfaces, and can further serve as template agents for microcapsule synthesis, maintaining the stability of the core material mixed droplets. Secondly, under the influence of high temperature, the crystal axis of the barium titanate nanoparticles will be distorted, leading to spontaneous polarization without any external electric field, generating permanent electrodes. On the one hand, during the synthesis of cuprous oxide in the microcapsule composite shell, copper ions can be adsorbed onto the surface of the polydopamine film, effectively increasing the copper ion loading of the microcapsule shell, thus generating a porous cuprous oxide structure with a large specific surface area during the subsequent copper ion reduction process. On the other hand, during application, the high temperature attracts compounds released by various asphalt building materials to the vicinity of the slow-release modified microcapsules, increasing the difficulty of these compounds volatilizing while allowing the cuprous oxide shell of the microcapsules to adsorb more harmful compounds, and causing the smoke-suppressing active components on the surface of the microcapsules to react with more of the above compounds, thereby effectively reducing the impact of irritating gases released by various asphalt building materials on the human body.

[0100] (2) The odor-neutralizing and temperature-controlled 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 various asphalt building materials. The second function is that after being synthesized by the method described in the present invention, cuprous oxide will form a porous structure with a large specific surface area on the surface of the microcapsule, which effectively improves the adsorption capacity of cuprous oxide for harmful substances in the flue gas of various asphalt building materials. The third function is that cuprous oxide has extremely strong catalytic activity, which can catalyze the reaction between the smoke-suppressing compounds on the surface of the odor-neutralizing and temperature-controlled microcapsule and pollutants, further improving the smoke-suppressing ability of the odor-neutralizing and temperature-controlled microcapsule.

[0101] (3) The odor-neutralizing and temperature-controlled microcapsules of the present invention can regulate the temperature of various asphalt building materials (such as asphalt pavement) in situ. They can not only effectively improve the high-temperature performance of asphalt building materials, but also reduce the damage caused by temperature changes to asphalt building materials and extend the service life of various asphalt building materials.

[0102] (4) The odor-neutralizing and temperature-controlled microcapsules of the present invention can reduce the temperature of asphalt building materials during application after being added to various asphalt building materials. This can not only effectively reduce the urban heat island effect, but also prevent various asphalt building materials from releasing various harmful substances due to excessive temperature, thereby avoiding the generation of photochemical smog and haze. Detailed Implementation

[0103] To further illustrate the technical solution of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0104] The hydrogen sulfide in the asphalt flue gas described in this invention was tested using a TESTO 350 flue gas analyzer.

[0105] The volatile organic compounds in the asphalt fumes described in this invention were tested using a Thermo Fisher TVA-2020 toxic volatile gas detector.

[0106] 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.

[0107] Example 1

[0108] (1): Preparation of barium titanate nanoparticles

[0109] S1: Weigh 20 parts by mass of tetrabutyl titanate and 15 parts by mass of methanol and add them to a flask. Stir for 3 hours at 25°C and 450 rpm to obtain a titanium precursor solution.

[0110] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 11.5, and continue stirring at 450 rpm for 3 hours at 25℃ to obtain the titanium precursor sol.

[0111] S3: Add 15.2 parts by mass of Ba(OH)2 and 16 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 4 hours at 95°C.

[0112] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 120℃, stir at 450 rpm for 18 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0113] 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 40 parts by mass of dimethylacetamide. Modify by stirring at 200 rpm for 4 hours at 120°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0114] (2): Heat 3 parts by mass of n-dodecane to melt at 50°C, add 50 parts by mass of formamide and 1 part by mass of barium titanate nanoparticles obtained in step (1), and stir for 5 hours at 50°C and 400 rpm.

[0115] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0116] (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 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then 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.

[0117] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 6.5 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0118] (6): 1.65 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 h at a temperature of 110°C.

[0119] (7): Add 5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution, and stir at 200 rpm for 1 h at 50 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h.

[0120] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10 using dilute potassium hydroxide solution, and stir for 2 hours at 70°C and 200 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2 parts by mass of chloropropyltriethoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0121] (9): 5 parts by mass of the smoke-suppressing compound 2-methylundecaldehyde and allyl ionone were stirred evenly and then added to 1 part by mass of the solid material obtained in step (8) in 50 parts by mass of anhydrous ethanol. Then 1 part by mass of KOH was added and the mixture was refluxed at 95°C for 6 hours. The bottom solid powder was then filtered and washed and vacuum dried at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules was 3.35-7.98 μm and the loading of the active smoke-suppressing compound accounted for 10.25 wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0122] 100 parts by weight of base asphalt (penetration 971 / 10mm at 25℃) is heated to 143℃, and 1.2 parts by weight of odor-neutralizing and temperature-controlled microcapsules are added at a speed of 500 rpm and stirred for 4 hours to obtain odor-neutralizing and temperature-controlled asphalt material.

[0123] Example 2

[0124] (1): Preparation of barium titanate nanoparticles

[0125] S1: Weigh 14 parts by mass of tetrabutyl titanate and 10 parts by mass of ethylene glycol and add them to a flask. Stir for 2 hours at 55°C and 400 rpm to obtain a titanium precursor solution.

[0126] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 12, and continue stirring at 400 rpm for 2 hours at 55℃ to obtain titanium precursor sol.

[0127] S3: Add 10.6 parts by mass of Ba(OH)2 and 12 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 3 hours at 90°C.

[0128] 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 15 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0129] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 5 parts by mass of dodecyl dimethyl benzyl ammonium chloride to 30 parts by mass of N,N-dimethylformamide. 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 30-50 nm).

[0130] (2): Heat 3 parts by mass of n-dodecane to melt at 50°C, add 50 parts by mass of formamide and 1 part by mass of barium titanate nanoparticles obtained in step (1), and stir for 5 hours at 50°C and 400 rpm.

[0131] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0132] (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 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then 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.

[0133] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 6.5 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0134] (6): 1.65 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 h at a temperature of 110°C.

[0135] (7): Add 5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution, and stir at 200 rpm for 1 h at 50 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h.

[0136] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10 using dilute potassium hydroxide solution, and stir for 2 hours at 70°C and 200 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2 parts by mass of chloropropyltriethoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0137] (9): Mix 5 parts by mass of the smoke-suppressing compound 10-undecenal and menthone in equal mass ratio, add 1 part by mass of the solid material obtained in step (8) to 50 parts by mass of methanol, then add 1 part by mass of KOH, and reflux at 85°C for 6 hours. Then filter and wash the bottom solid powder, and vacuum dry at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules is 3.35-7.98μm, and the loading of the active smoke-suppressing compound accounts for 10.25wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0138] 100 parts by weight of base asphalt (penetration 971 / 10mm at 25℃) is heated to 143℃, and 1.2 parts by weight of odor-neutralizing and temperature-controlled microcapsules are added at a speed of 500 rpm and stirred for 4 hours to obtain odor-neutralizing and temperature-controlled asphalt material.

[0139] Example 3

[0140] (1): Preparation of barium titanate nanoparticles

[0141] S1: Weigh 16 parts by mass of tetrabutyl titanate and 15 parts by mass of ethylene glycol and add them to a flask. Stir for 2 hours at 50°C and 450 rpm to obtain a titanium precursor solution.

[0142] S2: Slowly add 10wt% ammonia water to the S1 solution until the pH of the reaction system is 11.5, and continue stirring at 450 rpm for 2 hours at 50℃ to obtain titanium precursor sol.

[0143] S3: Add 12.3 parts by mass of Ba(OH)2 and 16 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 4 hours at 95°C.

[0144] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 140℃, stir at 450 rpm for 16 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0145] S5: Add 1 part by mass of the primary barium titanate nanoparticles obtained in step S4 and 5 parts by mass of hexadecyltrimethylammonium bromide to 40 parts by mass of dimethylacetamide. Modify by stirring at 300 rpm for 5 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 30-50 nm).

[0146] (2): 3 parts by mass of n-dodecane were heated and melted at 50°C, 50 parts by mass of N,N-dimethylformamide and 1 part by mass of barium titanate nanoparticles obtained in step (1) were added, and the mixture was stirred at 50°C and 400 rpm for 5 hours.

[0147] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0148] (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 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then 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.

[0149] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 6.5 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0150] (6): 1.65 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 h at a temperature of 110°C.

[0151] (7): Add 5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution, and stir at 200 rpm for 1 h at 50 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h.

[0152] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10 using dilute potassium hydroxide solution, and stir for 2 hours at 70°C and 200 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2 parts by mass of chloropropyltriethoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0153] (9): Three parts by mass of the smoke-suppressing compound 2-methylundecaldehyde and allyl ionone were stirred evenly and then added to 50 parts by mass of the solid material obtained in step (8). Then, 1 part by mass of KOH was added and the mixture was refluxed at 95°C for 6 hours. The bottom solid powder was then filtered and washed and vacuum dried at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules was 3.28-7.82 μm and the loading of the active smoke-suppressing compound accounted for 6.40 wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0154] 100 parts by weight of base asphalt (penetration 971 / 10mm at 25℃) is heated to 143℃, and 0.95 parts by weight of odor-neutralizing and temperature-controlled microcapsules are added at a speed of 500 rpm and stirred for 4 hours to obtain odor-neutralizing and temperature-controlled asphalt material.

[0155] Example 4

[0156] (1): Preparation of barium titanate nanoparticles

[0157] S1: Weigh 18 parts by mass of tetrabutyl titanate and 14 parts by mass of butanediol and add them to a flask. Stir at 45°C and 450 rpm for 3 hours to obtain a titanium precursor solution.

[0158] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 11, and continue stirring at 450 rpm for 3 hours at 45℃ to obtain the titanium precursor sol.

[0159] S3: Add 13.5 parts by mass of Ba(OH)2 and 14 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 4 hours at 95°C.

[0160] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 130℃, stir at 450 rpm for 17 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.

[0161] 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 40 parts by mass of dimethylacetamide. 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 30-50 nm).

[0162] (2): 3 parts by mass of n-eicosane were heated and melted at 50°C, and 50 parts by mass of formamide and 1 part by mass of barium titanate nanoparticles obtained in step (1) were added. The mixture was stirred at 50°C and 400 rpm for 5 hours.

[0163] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0164] (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 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then 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.

[0165] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 6.5 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0166] (6): 1.65 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 h at a temperature of 110°C.

[0167] (7): Add 5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution, and stir at 200 rpm for 1 h at 50 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h.

[0168] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10 using dilute potassium hydroxide solution, and stir for 2 hours at 70°C and 200 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2 parts by mass of chloropropyltriethoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0169] (9): 5 parts by mass of the smoke-suppressing compound 2-methylundecaldehyde and allyl ionone were stirred evenly and then added to 1 part by mass of the solid material obtained in step (8) in 50 parts by mass of anhydrous ethanol. Then 1 part by mass of KOH was added and the mixture was refluxed at 95°C for 6 hours. The bottom solid powder was then filtered and washed and vacuum dried at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules was 3.35 to 7.98 μm and the loading of the active smoke-suppressing compound accounted for 10.25 wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0170] 100 parts by weight of base asphalt (penetration 971 / 10mm at 25℃) is heated to 143℃, and 1.2 parts by weight of odor-neutralizing and temperature-controlled microcapsules are added at a speed of 500 rpm and stirred for 4 hours to obtain odor-neutralizing and temperature-controlled asphalt material.

[0171] Example 5

[0172] (1): Preparation of barium titanate nanoparticles

[0173] S1: Weigh 12 parts by mass of tetrabutyl titanate and 10 parts by mass of methanol and add them to a flask. Stir for 2 hours at 25°C and 450 rpm to obtain a titanium precursor solution.

[0174] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 10, and continue stirring at 450 rpm for 2 hours at 25℃ to obtain titanium precursor sol.

[0175] 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 4 hours at 95°C.

[0176] 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 14 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.

[0177] 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 40 parts by mass of dimethylacetamide. Modify by stirring at 200 rpm for 4 hours at 120°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0178] (2): Heat 3 parts by mass of n-dodecane to melt at 50°C, add 50 parts by mass of formamide and 1 part by mass of barium titanate nanoparticles obtained in step (1), and stir for 5 hours at 50°C and 400 rpm.

[0179] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0180] (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 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then 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.

[0181] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 6.5 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0182] (6): Mix 1.2 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water by manual stirring at room temperature to prepare a copper sulfate solution. Add 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution to the reactor, close the reactor lid, and stir at 200 rpm for 1 hour at 110°C.

[0183] (7): Add 5 parts by mass of potassium sulfite to 50 parts by mass of pH=6 acetate buffer solution, and stir at 200 rpm for 1 h at 50 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h.

[0184] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10 using dilute potassium hydroxide solution, and stir for 2 hours at 70°C and 200 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2 parts by mass of chloropropyltriethoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0185] (9): 5 parts by mass of the smoke-suppressing compound 2-methylundecaldehyde and allyl ionone were stirred evenly and then added to 1 part by mass of the solid material obtained in step (8) in 50 parts by mass of anhydrous ethanol. Then 1 part by mass of KOH was added and the mixture was refluxed at 95°C for 6 hours. The bottom solid powder was then filtered and washed and vacuum dried at -30°C for 5 hours to obtain the odor-neutralizing temperature-controlled microcapsules. The particle size of the microcapsules was 3.18-7.57 μm and the loading of the active smoke-suppressing compound accounted for 7.85 wt% of the total mass of the odor-neutralizing temperature-controlled microcapsules.

[0186] 100 parts by weight of base asphalt (penetration 971 / 10mm at 25℃) is heated to 143℃, and 1.05 parts by weight of odor-neutralizing and temperature-controlled microcapsules are added at a speed of 500 rpm and stirred for 4 hours to obtain odor-neutralizing and temperature-controlled asphalt material.

[0187] Comparative Example 1

[0188] 100 parts of base asphalt (25℃ penetration 971 / 10mm) were heated to 143℃ and stirred at 500 rpm for 4 hours to obtain the base asphalt control sample.

[0189] Comparative Example 2

[0190] (1): Preparation of barium titanate nanoparticles

[0191] S1: Weigh 20 parts by mass of tetrabutyl titanate and 15 parts by mass of methanol and add them to a flask. Stir for 3 hours at 25°C and 450 rpm to obtain a titanium precursor solution.

[0192] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 11.5, and continue stirring at 450 rpm for 3 hours at 25℃ to obtain the titanium precursor sol.

[0193] S3: Add 15.2 parts by mass of Ba(OH)2 and 16 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 4 hours at 95°C.

[0194] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 120℃, stir at 450 rpm for 18 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0195] 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 40 parts by mass of dimethylacetamide. Modify by stirring at 200 rpm for 4 hours at 120°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0196] (2): Heat 3 parts by mass of n-dodecane to melt at 50°C, add 50 parts by mass of formamide and 1 part by mass of barium titanate nanoparticles obtained in step (1), and stir for 5 hours at 50°C and 400 rpm.

[0197] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0198] (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 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then stop stirring and keep the temperature constant for 24 hours. Then filter and wash the solid powder in the reaction system and vacuum dry the solid powder at -30°C for 5 hours.

[0199] 100 parts by weight of base asphalt (25℃, penetration 971 / 10mm) is heated to 143℃, and 1.2 parts by weight of the solid powder obtained in step (4) is added at a speed of 500 rpm. The mixture is stirred for 4 hours to obtain the comparison asphalt sample.

[0200] Comparative Example 3

[0201] (1): Preparation of barium titanate nanoparticles

[0202] S1: Weigh 20 parts by mass of tetrabutyl titanate and 15 parts by mass of methanol and add them to a flask. Stir for 3 hours at 25°C and 450 rpm to obtain a titanium precursor solution.

[0203] S2: Slowly add 10wt% ammonia to the S1 solution until the pH of the reaction system is 11.5, and continue stirring at 450 rpm for 3 hours at 25℃ to obtain the titanium precursor sol.

[0204] S3: Add 15.2 parts by mass of Ba(OH)2 and 16 parts by mass of deionized water to the reactor, and heat and stir at 400 rpm for 4 hours at 95°C.

[0205] S4: Add the sol obtained in S2 to the reaction vessel in S3, close the reaction vessel lid, heat to 120℃, stir at 450 rpm for 18 hours, then filter and wash the solid powder in the reaction system, and vacuum dry at -30℃ for 5 hours. After grinding until there are no obvious lumps in the system, the primary barium titanate nanoparticles are obtained.

[0206] 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 40 parts by mass of dimethylacetamide. Modify by stirring at 200 rpm for 4 hours at 120°C. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain barium titanate nanoparticles (particle size of 30-50 nm).

[0207] (2): Heat 3 parts by mass of n-dodecane to melt at 50°C, add 50 parts by mass of formamide and 1 part by mass of barium titanate nanoparticles obtained in step (1), and stir for 5 hours at 50°C and 400 rpm.

[0208] (3): Keeping the conditions of the reaction system in step (2) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (2). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0209] (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 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then 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.

[0210] (5): Add the solid material obtained in step (4) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 6.5 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0211] (6): 1.65 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (5) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 h at a temperature of 110°C.

[0212] (7): Add 5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution, and stir at 200 rpm for 1 h at 50 °C; add the prepared mixed solution to the reaction vessel in step (6), close the vessel lid, stir at 200 rpm for 4 h at 90 °C, and finally filter and wash the bottom solid powder, and vacuum dry at -30 °C for 5 h.

[0213] (8): Add 1 part by mass of the solid particles obtained in step (7) to 30 parts by mass of deionized water, then adjust the pH of the system to 10 using dilute potassium hydroxide solution, and stir for 2 hours at 70°C and 200 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2 parts by mass of chloropropyltriethoxysilane to the reaction system in step (8), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours to obtain solid powder.

[0214] Heat 100 parts by weight of base asphalt (25℃, penetration 971 / 10mm) to 143℃, add 1.2 parts by weight of the solid powder obtained in step (8) at a speed of 500 rpm, and stir for 4 hours to obtain the control asphalt sample.

[0215] Comparative Example 4

[0216] (1): 3 parts by mass of n-dodecane were heated and melted at 50°C, 50 parts by mass of formamide and 1 part by mass of hexadecyltrimethylammonium bromide were added, and the mixture was stirred at 50°C and 400 rpm for 5 hours.

[0217] (2): Keeping the conditions of the reaction system in step (1) unchanged, slowly add 3 parts by mass of tetraethyl orthosilicate to the reaction system in step (1). After the addition is completed, continue stirring at 50°C and 400 rpm for 5 hours to obtain Pickering emulsion.

[0218] (3): Slowly add 10wt% dilute hydrochloric acid to the reaction system in step (2) using a peristaltic pump until the pH of the reaction system is 3.5. Continue stirring at 400 rpm for 5 hours at 50°C, then 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.

[0219] (4): Add the solid material obtained in step (3) to a Tris buffer solution with a pH of 8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 6.5 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0220] (5): 1.65 parts by mass of anhydrous copper sulfate and 80 parts by mass of deionized water were manually stirred and mixed at room temperature to prepare a copper sulfate solution. 1 part by mass of the solid particles obtained in step (4) and the prepared copper sulfate solution were added to the reactor, the reactor lid was closed, and the mixture was stirred at 200 rpm for 1 h at a temperature of 110°C.

[0221] (6): Add 5 parts by mass of sodium sulfite to 50 parts by mass of pH=6 acetate buffer solution, and stir at 200 rpm for 1 h at 50 °C; add the prepared mixed solution to the reaction vessel in step (5), 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.

[0222] (7): Add 1 part by mass of the solid particles obtained in step (6) to 30 parts by mass of deionized water, then adjust the pH of the system to 10 using dilute potassium hydroxide solution, and stir for 2 hours at 70°C and 200 rpm. Keeping the temperature and stirring conditions unchanged, slowly add 2 parts by mass of chloropropyltriethoxysilane to the reaction system in step (7), and continue stirring for 2 hours. Finally, filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0223] (8): Mix 5 parts by mass of the smoke-suppressing compound 2-methylundecaldehyde and allyl ionone in equal mass ratio, and add 1 part by mass of the solid material obtained in step (7) into 50 parts by mass of anhydrous ethanol. Then add 1 part by mass of KOH and reflux at 95°C for 6 hours. Then filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours to obtain the solid powder.

[0224] Heat 100 parts by weight of base asphalt (25℃, penetration 971 / 10mm) to 143℃, add 1.2 parts by weight of the solid powder obtained in step (8) at a speed of 500 rpm and stir for 4 hours to obtain environmentally friendly, odorless asphalt.

[0225] Test Example 1

[0226] Hydrogen sulfide and hydrocarbon compounds are harmful substances that are produced during the service of asphalt pavement and have a significant impact on human health. The asphalt samples prepared in Examples 1-5 and Comparative Examples 1-4 were enriched in flue gas at a temperature of 145°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.

[0227] Table 1

[0228] Test sample Hydrogen sulfide content, ppm <![CDATA[Total non-methane hydrocarbon content, mg·m- 3 > Example 1 199.54 1123.74 Example 2 213.67 1191.84 Example 3 285.19 1408.58 Example 4 266.05 1328.06 Example 5 270.93 1406.42 Comparative Example 1 831.40 3405.27 Comparative Example 2 640.18 2962.58 Comparative Example 3 590.29 2758.27 Comparative Example 4 557.04 2622.06

[0229] Test Example 2

[0230] The asphalt samples prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to flue gas enrichment at a temperature of 50°C for 48 hours. After enrichment, the gas in the sealed container was extracted and tested. The data obtained are shown in Table 2 below.

[0231] Table 2

[0232]

[0233]

[0234] 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. A deodorizing and temperature-controlled microcapsule, characterized in that, The odor-neutralizing and temperature-controlled microcapsule comprises a composite shell and a core material. The composite shell comprises an inorganic base shell, barium titanate nanoparticles, polydopamine, and cuprous oxide. The core material comprises n-alkanes with a phase transition temperature of 40-60°C. The surface of the composite shell is loaded with an active smoke-suppressing compound.

2. The odor-neutralizing and temperature-controlled microcapsule according to claim 1, characterized in that, The particle size of the odor-neutralizing and temperature-controlled microcapsules is 1-12 μm.

3. The odor-neutralizing and temperature-controlled microcapsule according to claim 1, characterized in that, The mass ratio of the composite shell material to the core material of the odor-neutralizing and temperature-controlled microcapsule is 1:(0.2-2); And / or, the composite shell material comprises an inorganic base shell / barium titanate nanoparticles / polydopamine / cuprous oxide, wherein the mass ratio of the inorganic base shell to the barium titanate nanoparticles is 1:(0.2-0.8), the mass ratio of the inorganic base shell to the polydopamine is 1:(0.1-0.5), and the mass ratio of the inorganic base shell to the cuprous oxide is 1:(0.5-2); And / or, the material of the inorganic base shell is selected from at least one of silicon dioxide and titanium dioxide, preferably silicon dioxide; And / or, the n-alkane with a phase transition temperature of 40-60°C is one or more of n-octadecane, n-eicosane, and n-docosahexadecane.

4. The odor-neutralizing and temperature-controlled microcapsule according to claim 1, characterized in that, The loading of the active smoke-suppressing compound accounts for 0.1wt%-20wt% of the total mass of the odor-neutralizing and temperature-controlled microcapsules; And / or, the active smoke-suppressing compound is selected from one or more aldehyde compounds with a molecular weight greater than 160 and / or ketone compounds with a molecular weight greater than 150.

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

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

13. The method according to claim 5, characterized in that, In step (3), the inorganic base shell precursor is at least one of silicate ester compounds and titanate ester compounds, preferably a silicate ester compound; the silicate ester compound is preferably at least one of methyl silicate, tetraethyl orthosilicate, tetraethyl orthosilicate, and tetrabutyl orthosilicate. And / or, in step (3), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours.

14. The method according to claim 5, characterized in that, In step (4), adjust the pH value to 3-6; And / or, in step (4), the stirring speed is 400-600 rpm, the stirring temperature is 40-80℃, and the stirring time is 4-6 hours; And / or, in step (4), the aging conditions are: standing at 40-80°C for 12-30 hours.

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

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

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

18. The method according to claim 5, characterized in that, In step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-6h; And / or, in step (8), adjust the pH to 9-11; And / or, in step (8), the mass ratio of the solid particles obtained in step (7) to water is 1:(10-50); And / or, in step (8), the added silane coupling agent is selected from one or more of chloropropyltriethoxysilane, chloromethyltriethoxysilane, dichloromethyltriethoxysilane, and chloromethyltriisopropoxysilane; And / or, in step (8), the mass ratio of the solid particles obtained in step (7) to the silane coupling agent is 1:(0.5-4); And / or, in step (8), the stirring speed is 300-500 rpm, the stirring temperature is 20-90℃, and the stirring time is 1-8h.

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

20. The application of the odor-neutralizing and temperature-controlled microcapsules according to any one of claims 1-4 or the odor-neutralizing and temperature-controlled microcapsules prepared by the method according to any one of claims 5-19 in odor-neutralizing and temperature-controlled asphalt materials, wherein the odor-neutralizing and temperature-controlled asphalt materials comprise, by weight, the following components: The odor-neutralizing and temperature-controlled microcapsules: 0.1-10 parts, preferably 1.2-3 parts. Base asphalt: 50-200 parts.

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