Insect-repellent environment-friendly microcapsule, insect-repellent environment-friendly asphalt additive and preparation method thereof

Abstract

The application discloses an environmentally-friendly insect-repelling microcapsule, an environmentally-friendly insect-repelling asphalt additive and a preparation method thereof. The shell material of the environmentally-friendly insect-repelling microcapsule is a composite shell material comprising silicon dioxide / nano-electric jade, and the core material comprises one or more of a pyrethrum compound, a carboxylic acid ester compound, an amide compound and a plant extract; the shell material is loaded with a metal chelate on the surface. The environmentally-friendly insect-repelling microcapsule can not only efficiently and durably repel insects around roads, but also effectively inhibit the amount of pollutants generated by high-temperature action of asphalt in the production, construction and pavement process, thereby providing a new idea for functional utilization of asphalt materials.

Description

Technical Field

[0001] This invention belongs to the field of special asphalt, specifically relating to an insect-repellent and environmentally friendly microcapsule, an insect-repellent and environmentally friendly asphalt additive, and their preparation method. Background Technology

[0002] With the rapid development of road engineering in China, the total mileage of expressways in China has reached the forefront of the world in recent years. However, some problems remain unresolved during the operation of expressways. First, the number of insects increases significantly in summer and autumn, and some insects' activity range extends to some expressways, causing vehicles to collide with large numbers of insects while traveling at high speeds. This results in a large amount of insect carcasses adhering to the windshields, which are difficult to clean, seriously obstructing the driver's vision and endangering driving safety. Second, during the hot construction and service of asphalt pavements, the high temperatures released by the pavement release toxic, harmful, and irritating gases, which not only pollute the environment but also affect human health and cause discomfort.

[0003] CN115678289A discloses an anti-shedding sulfur asphalt, its preparation method, and its application. This method involves adding a large amount of sulfur to the asphalt, causing it to release a large amount of the characteristic pungent odor of sulfur during road surface service, thereby repelling insects. However, the sulfur odor released by the asphalt products produced using this method, while repelling insects, can also cause discomfort to humans. Furthermore, the asphalt products mentioned in this method release more toxic and irritating gases during production, construction, and road application than ordinary base asphalt, which contradicts the green and low-carbon development strategy.

[0004] Therefore, there is an urgent need to develop a road surface material that can effectively suppress the release of toxic gases from asphalt and prevent insect infestations, thereby achieving the dual goals of driving safety and environmental protection. Summary of the Invention

[0005] To address the problems existing in the prior art, this invention provides an insect-repellent and environmentally friendly microcapsule, an insect-repellent and environmentally friendly asphalt additive, and their preparation method. The insect-repellent and environmentally friendly microcapsule of this invention can not only efficiently and persistently repel insects around roads, but also effectively inhibit the amount of pollutants generated by asphalt under high temperatures during production, construction, and road surface use, providing a completely new approach to the functional utilization of asphalt materials.

[0006] The first aspect of the present invention provides an insect-repellent and environmentally friendly microcapsule, wherein the shell material is a composite shell material comprising silica / nano-tourmaline, and the core material comprises one or more of pyrethroid compounds, carboxylic acid ester compounds, amide compounds, and plant extracts; the surface of the shell material is loaded with metal chelates.

[0007] Furthermore, the diameter of the insect-repellent and environmentally friendly microcapsules is 1-3 μm.

[0008] Furthermore, the mass ratio of the shell material to the core material of the insect-repellent and environmentally friendly microcapsule is 1:(0.8-2.0).

[0009] Furthermore, the core material of the insect-repellent and environmentally friendly microcapsule preferably includes pyrethroid compounds, carboxylic acid ester compounds, amide compounds, and plant extracts.

[0010] Furthermore, the pyrethroid compound has >18 carbon atoms; preferably, it is one or more of cypermethrin, bifenthrin, deltamethrin, cypermethrin, ethionylmethrin, deltamethrin, and methamidophos.

[0011] Further, the carboxylic acid ester has >9 carbon atoms; preferably, it is one or more of ethyl butyl acetaminopropionate, hexyl diethylcarbamoyl carboxylate, butyl 3-methylquinoline-4-carboxylate, dibutyl succinate, and dipropyl 2,5-pyridinedicarboxylate.

[0012] Furthermore, the amide compound has >10 carbon atoms; preferably one or more of N,N-diethyl-3-methylbenzamide, ethylhexylbicycloheptenedicarboximide, and N,N-diethylbenzamide.

[0013] Furthermore, the plant extract has >9 carbon atoms; preferably one or more of camphor and borneol.

[0014] Furthermore, the shell material is a silica / nano-tourmaline composite shell material, wherein the mass ratio of silica to nano-tourmaline is (1-5):1.

[0015] Furthermore, the shell material surface is loaded with a metal chelate, wherein the metal is preferably copper. The chelating agent for the metal chelation is preferably at least one selected from iminodiacetic acid, triethylenediamine, and hypozinotriacetic acid, and more preferably iminodiacetic acid.

[0016] Furthermore, the shell material surface is loaded with metal chelates, and the metal loading accounts for 0.1wt%-10wt% of the total mass of the insect-repellent and environmentally friendly microcapsules.

[0017] A second aspect of this invention provides a method for preparing insect-repellent and environmentally friendly microcapsules, comprising the following steps:

[0018] S1: Mix nano-tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze dry to obtain modified nano-tourmaline powder;

[0019] S2: Mix one or more of the following: pyrethroids, lipids, amides, and plant extracts to obtain a core material mixture;

[0020] S3: Add solvent and modified nano-tourmaline powder obtained in step S1 to the core material mixture obtained in step S2, and stir to mix;

[0021] S4: Add the shell material precursor to the reaction system of step S3, stir and mix to obtain Pickering emulsion;

[0022] S5: Adjust the pH of the Pickering emulsion obtained in step S4 to 3-6, continue stirring, then age, filter, freeze dry, and obtain the insect-repellent and environmentally friendly microcapsule matrix;

[0023] S6: Disperse the insect-repellent and environmentally friendly microcapsule matrix obtained in step S5 in a methanol dispersion, then add a coupling agent methanol solution, adjust the pH of the reaction system to 9-11, process under stirring, then filter, wash, and freeze dry.

[0024] S7: Disperse the solid powder obtained after freeze-drying in step S6 in a buffer solution, add a chelating agent, process under stirring, filter, wash, and freeze-dry.

[0025] S8: Disperse the solid powder obtained after freeze-drying in step S7 in a metal ion salt-formamide solution, and process it under stirring. After the reaction is complete, filter, wash, and freeze-dry to obtain insect-repellent and environmentally friendly microcapsules.

[0026] Furthermore, in step S1, the particle size of the nano-tourmaline powder is 10-100 nm.

[0027] Further, in step S1, the surfactant is a cationic surfactant, preferably at least one of hexadecyltrimethylammonium bromide (CTAB), dodecyl dimethyl benzyl ammonium chloride, and octadecyltrimethylammonium chloride, and more preferably hexadecyltrimethylammonium bromide (CTAB).

[0028] Further, in step S1, 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.

[0029] Further, in step S1, the mass ratio of the nano-tourmaline powder to the surfactant is (1-10):1, and the mass ratio of the solvent to the surfactant is (20-40):1.

[0030] Further, in step S1, the stirring speed is 400-600 rpm; the modification temperature is 100-200℃; and the modification time is 4-8 hours.

[0031] Furthermore, in step S1, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0032] Furthermore, in step S2, the stirring speed is 400-600 rpm, the stirring temperature is 40-60°C, and the stirring time is 3-10 minutes.

[0033] Further, in step S3, 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.

[0034] Further, in step S3, the mass ratio of the core material mixture to the modified nano-tourmaline powder is (1-10):1; the mass ratio of the solvent to the modified nano-tourmaline powder is (20-40):1.

[0035] Furthermore, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours.

[0036] Further, in step S4, the shell material precursor is a silicate ester compound, preferably at least one of methyl silicate, ethyl orthosilicate, tetraethyl orthosilicate, and butyl orthosilicate, and more preferably ethyl orthosilicate.

[0037] Further, in step S4, the mass ratio of the core material mixture to the shell material precursor is (0.5-2):1. The stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours.

[0038] Furthermore, in step S5, 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 40-60℃, and the stirring time is 4-6 hours.

[0039] Further, in step S5, 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.

[0040] Furthermore, in step S6, the insect-repellent and environmentally friendly microcapsule matrix is ​​dispersed in methanol, which can be achieved by ultrasonic dispersion.

[0041] Further, in step S6, the coupling agent is a silane coupling agent, preferably at least one of 3-chloropropyltrimethylsilane, (dichloromethyl)trimethylsilane, (trichloromethyl)trimethylsilane, and (chlorodifluoromethyl)trimethylsilane, and more preferably 3-chloropropyltrimethylsilane.

[0042] Further, in step S6, the coupling agent methanol solution is prepared by combining the coupling agent and methanol, with a mass ratio of methanol to coupling agent of (10-15):1.

[0043] Further, in step S6, the mass ratio of the methanol dispersion to the insect-repellent and environmentally friendly microcapsule matrix is ​​(10-20):1. The mass ratio of the insect-repellent and environmentally friendly microcapsule matrix to the coupling agent methanol solution is (1-15):1.

[0044] Furthermore, in step S6, the pH can be adjusted using an alkaline solution, such as ammonia.

[0045] Furthermore, in step S6, the stirring speed is 200-450 rpm; the processing temperature is 40-60℃; and the processing time is 4-6 hours.

[0046] Furthermore, in step S6, the reaction is carried out under the protection of nitrogen or an inert gas.

[0047] Furthermore, in step S6, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8 hours.

[0048] Furthermore, in step S7, the solid powder obtained after lyophilization in step S6 can be dispersed in a buffer solution by ultrasonic dispersion.

[0049] Furthermore, the buffer solution mentioned in step S7 is preferably one of phosphate buffer and carbonate buffer, and more preferably carbonate buffer.

[0050] Further, in step S7, the pH value of the buffer solution is 9-11.

[0051] Further, in step S7, the mass ratio of the buffer solution to the solid powder obtained after lyophilization in step S6 is (15-20):1.

[0052] Further, in step S7, the chelating agent has a ligand tooth number >2, preferably iminodiacetic acid, triethylenediamine, or hypozinotriacetic acid, and more preferably iminodiacetic acid.

[0053] Further, in step S7, the mass ratio of the solid powder obtained after freeze-drying in step S6 to the chelating agent is (10-15):1.

[0054] Furthermore, in step S7, the stirring speed is 200-450 rpm, the processing temperature is 40-60℃, and the processing time is 2-5 hours.

[0055] Furthermore, in step S7, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8 hours.

[0056] Furthermore, in step S8, the solid powder obtained after drying in step S7 is dispersed in a metal ion salt-formamide solution, which can be done by ultrasonic dispersion.

[0057] Furthermore, in step S8, the metal ion salt is preferably a copper ion salt, and more preferably anhydrous copper sulfate.

[0058] Further, in step S8, the mass ratio of the metal ion salt to formamide in the metal ion salt-formamide solution is (0.5-1.5):1.

[0059] Further, in step S8, the mass ratio of the metal ion salt-formamide solution to the solid powder obtained after drying in step S7 is (5-15):1.

[0060] Furthermore, in step S8, the stirring speed is 200-450 rpm, the processing temperature is 100-180℃, and the processing time is 2-5 hours.

[0061] Furthermore, in step S8, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8 hours.

[0062] A third aspect of this invention provides an insect-repellent and environmentally friendly asphalt additive, comprising the following components by weight:

[0063] The above-mentioned insect-repellent and environmentally friendly microcapsules, 1-10 portions;

[0064] Dispersant, 1-10 parts.

[0065] Furthermore, the dispersant is one of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

[0066] Furthermore, the dispersant and the insect-repellent and environmentally friendly microcapsules are stirred and mixed at room temperature at a speed of 200-400 rpm for 1-3 hours to obtain the insect-repellent and environmentally friendly asphalt additive.

[0067] A fourth aspect of the present invention provides an insect-repellent and environmentally friendly asphalt, comprising the following components by weight:

[0068] Base bitumen, 100-300 parts;

[0069] The above-mentioned insect-repellent and environmentally friendly asphalt additive, 1-50 parts.

[0070] Further, the base asphalt is heated to 133-153℃, and the insect-repellent environmentally friendly asphalt additive is added at a speed of 200-400 rpm. After stirring for 2-4 hours, the insect-repellent environmentally friendly asphalt can be obtained.

[0071] Compared with the prior art, the present invention has the following advantages:

[0072] (1) The insect-repellent and environmentally friendly microcapsule of the present invention has a shell material comprising a composite shell material of silica / nano-tourmaline. In the preparation process of the insect-repellent and environmentally friendly microcapsule, tourmaline powder can replace the template agent in the synthesis of microcapsules to maintain the stability of the microcapsule core material droplets. In addition, in the process of metal ion modification of the shell material, the negative ion field released by tourmaline can adsorb a large number of metal ions onto the surface of the microcapsule, effectively increasing the loading of transition metal ions in the shell material of the microcapsule. This can react chemically with the sulfides released by the asphalt pavement under high temperature, effectively reducing the malodorous gases released by the asphalt under high temperature and sunlight, and avoiding discomfort to the human body caused by the asphalt pavement. Furthermore, during the service of the road, after the insect-repellent and environmentally friendly microcapsule is heated, the nano-tourmaline powder contained inside the shell material will release a negative ion field, further attracting the compounds released by the asphalt pavement under high temperature to the vicinity of the insect-repellent and environmentally friendly microcapsule. While increasing the difficulty of volatilization of these compounds, it can also make the metal ions on the surface of the microcapsule react with more of the above compounds, further inhibiting their volatilization, thereby effectively reducing the impact of the irritating gases released by the asphalt pavement on the human body.

[0073] (2) The insect-repellent and environmentally friendly asphalt of the present invention contains insect-repellent and environmentally friendly microcapsules, the shell of which is modified with a layer of chelated metal ions by surface modification technology. This layer of chelated metal ions has empty orbitals. After the microcapsules enter the asphalt system, the chelated metal ions can directly accept the unshared electrons of some more active sulfur-containing and nitrogen-containing pollutants in the asphalt and form coordinate bonds, so as to stably fix the above compounds on the surface of the microcapsules, avoid their high-temperature volatilization, and further rapidly reduce the content of irritating gases in the asphalt fumes.

[0074] (3) The insect-repellent environmentally friendly asphalt of the present invention contains insect-repellent environmentally friendly microcapsules, which encapsulate insect-repellent components with low boiling points in a silica / nano-tourmaline composite shell. These active components can be slowly released from the microcapsules during the application of asphalt pavement, keeping insects away from the pavement area and avoiding the impact of insects on pedestrian and vehicle safety. It also has a long-lasting insect-repellent effect and can avoid repeated construction. Attached Figure Description

[0075] Figure 1 This is a scanning electron microscope image of the insect-repellent and environmentally friendly microcapsules obtained in Example 1. Detailed Implementation

[0076] To further illustrate the relevant features and technical means of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0077] The morphology of the insect-repellent and environmentally friendly microcapsules of this invention was tested using a scanning electron microscope with an accelerating voltage of 20KV. Since the microcapsule wall material is non-conductive, the samples need to be sputter-coated with gold before testing.

[0078] The insect-repellent and environmentally friendly microcapsules of the present invention were subjected to surface elemental testing using an X-ray energy dispersive spectroscopy (EDS) instrument to confirm that metal ions were successfully modified onto the surface of the microcapsules.

[0079] The smoke suppression effect of the insect-repellent and environmentally friendly asphalt of this invention was tested using a VOC detector with an FID detector and a smoke detector with an H2S electrochemical sensor.

[0080] In this invention, the insect-repelling effect is evaluated using the following method:

[0081] Insect-repellent and environmentally friendly asphalt was prepared into test blocks, which were placed in an open area of ​​a park. The volume of the test blocks was 300mm*300mm*50mm, and the test area was 100m². 3 The test area was monitored and recorded using cameras.

[0082] The base asphalt used in the following examples and comparative examples is Sinopec Donghai brand No. 70 Grade A asphalt.

[0083] Example 1

[0084] Preparation of insect-repellent and environmentally friendly microcapsules:

[0085] S1: Add tourmaline powder with a particle size of 50nm, hexadecyltrimethylammonium bromide (CTAB), and formamide to the first container. The mass ratio of tourmaline powder, hexadecyltrimethylammonium bromide (CTAB), and formamide is 1:1:30. Stir the mixture at 400 rpm for 5 hours at 160℃ to modify the surface of the nano-tourmaline powder. After the reaction is complete, wash the modified nano-tourmaline powder with ethanol several times and vacuum dry it at -30℃ for 5 hours for later use.

[0086] S2: Add bifenthrin, ethyl butyl acetaminopropionate, ethylhexyl dicycloheptendicarboximide, and camphor in equal mass ratio to the second container, and stir at 400 rpm for 5 minutes at 50°C to obtain the core material mixture.

[0087] S3: Add modified nano tourmaline powder and formamide. The mass ratio of the core material mixture, modified nano tourmaline powder and formamide is 4:1:30. Continue stirring at 400 rpm for 5 hours at 50°C.

[0088] S4: Add tetraethyl orthosilicate to the above reaction system. 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.

[0089] S5: Slowly add 10wt% dilute hydrochloric acid to the above reaction system using a peristaltic pump until the pH of the reaction system is 4. Continue stirring at 400 rpm for 5 hours at 50°C, then stop stirring and age at the same temperature for 24 hours. Then filter and wash the solid in the reaction system and vacuum dry at -30°C for 5 hours to obtain the insect-repellent and environmentally friendly microcapsule matrix.

[0090] S6: The insect-repellent and environmentally friendly microcapsule matrix obtained in step S5 was ultrasonically dispersed in methanol, and then 10 wt% 3-chloropropyltrimethylsilane methanol solution was added dropwise. The pH value was adjusted to 11 with ammonia water. The reaction was stirred for 5 hours at 400 rpm and 60°C. The mass ratio of methanol, insect-repellent microcapsule matrix and 3-chloropropyltrimethylsilane methanol solution was 10:1:1. The entire reaction was carried out under nitrogen protection. After stirring, the solid powder was filtered, washed, and vacuum dried at -30°C for 5 hours.

[0091] S7: The solid powder obtained in S6 was ultrasonically dispersed in a carbonate buffer solution with pH=11, and then iminodiacetic acid was added. The mass ratio of carbonate buffer solution, solid powder and iminodiacetic acid was 150:10:1. The mixture was stirred for 5 hours at 400 rpm and 50°C. After stirring, the solid powder was filtered, washed and vacuum dried at -30°C for 5 hours.

[0092] S8: The solid powder obtained in S7 was ultrasonically dispersed in a 50 wt% anhydrous copper sulfate-formamide solution. The mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution was 1:10. The mixture was stirred at 400 rpm and 140°C for 5 hours. After stirring, the solid powder was filtered, washed, and vacuum dried at -30°C for 5 hours to obtain the insect-repellent and environmentally friendly microcapsules. The electron micrograph is shown below. Figure 1 .

[0093] The insect-repellent and environmentally friendly microcapsules obtained in step S8 and dodecyl dimethyl betaine were stirred and mixed at 300 rpm for 3 hours at room temperature to obtain an insect-repellent and environmentally friendly asphalt additive. The mass ratio of the insect-repellent and environmentally friendly microcapsules to dodecyl dimethyl betaine was 1:1.

[0094] Heat 100 parts of base asphalt to 143°C, add 10 parts by weight of the above-mentioned insect-repellent environmentally friendly asphalt additive at 400 rpm, and stir for 4 hours to obtain insect-repellent environmentally friendly asphalt.

[0095] Example 2

[0096] Except for step S2, which involves adding equal mass ratios of deltamethrin, 3-methylquinoline-4-carboxylate butyl ester, N,N-diethyl-3-methylbenzamide, and borneol to the second container, the rest of the steps are the same as in Example 1.

[0097] Example 3

[0098] Except that the amount of insect-repellent and environmentally friendly asphalt additive used in the preparation of insect-repellent and environmentally friendly asphalt is 5 parts by weight, the rest is the same as in Example 1.

[0099] Example 4

[0100] Except that the dispersant used in the preparation of the insect-repellent and environmentally friendly asphalt additive is 1-hydroxyethyl-carboxymethyl-alkylimidazoline, the rest is the same as in Example 1.

[0101] Example 5

[0102] Except that the mass ratio of the core material mixture, modified nano-tourmaline powder, and formamide in step S3 is 5:1:30, the rest is the same as in Example 1.

[0103] Example 6

[0104] Except for the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution in step S8 being 1:8, the rest is the same as in Example 1.

[0105] Comparative Example 1

[0106] 100 parts of base asphalt were heated to 143°C, and 5 parts by mass of dodecyl dimethyl betaine were added at 400 rpm. The mixture was stirred for 4 hours to obtain an asphalt sample.

[0107] Comparative Example 2

[0108] Preparation of insect-repellent and environmentally friendly microcapsules:

[0109] S1: Add bifenthrin, ethyl butyl acetaminopropionate, ethylhexyl bicycloheptenediamine, and camphor in equal mass ratio to the first container, and stir at 400 rpm for 5 minutes at 50°C to obtain the core material mixture.

[0110] S2: Add hexadecyltrimethylammonium bromide and formamide. The mass ratio of the core material mixture, hexadecyltrimethylammonium bromide and formamide is 6:1:30. Continue stirring at 400 rpm for 5 hours at 50°C.

[0111] S3: Add tetraethyl orthosilicate to the above reaction system. 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.

[0112] S4: Slowly add 10wt% dilute hydrochloric acid to the above reaction system using a peristaltic pump until the pH of the reaction system is 4. Continue stirring at 400 rpm for 5 hours at 50°C, then stop stirring and age at the same temperature for 24 hours. Then filter and wash the solid in the reaction system and vacuum dry at -30°C for 5 hours to obtain the insect-repellent and environmentally friendly microcapsule matrix.

[0113] S5: The insect-repellent and environmentally friendly microcapsule matrix obtained in step S4 was ultrasonically dispersed in methanol, and then 10 wt% 3-chloropropyltrimethylsilane methanol solution was added dropwise. The pH value was adjusted to 11 with ammonia water. The reaction was stirred for 5 hours at 400 rpm and 60°C. The mass ratio of methanol, insect-repellent and environmentally friendly microcapsule matrix and 3-chloropropyltrimethylsilane methanol solution was 10:1:1. The reaction was carried out under nitrogen protection throughout. After stirring, the solid powder was filtered, washed, and vacuum dried at -30°C for 5 hours.

[0114] S6: The solid powder obtained in S5 was ultrasonically dispersed in a carbonate buffer solution with pH=11, and then iminodiacetic acid was added. The mass ratio of carbonate buffer solution, solid powder and iminodiacetic acid was 150:10:1. The mixture was stirred for 5 hours at 400 rpm and 50°C. After stirring, the solid powder was filtered, washed and vacuum dried at -30°C for 5 hours.

[0115] S7: The solid powder obtained in S6 is ultrasonically dispersed in a 50wt% anhydrous copper sulfate-formamide solution. The mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution is 1:10. The mixture is stirred at 400 rpm and 140℃ for 5 hours. After stirring, the solid powder is filtered, washed, and vacuum dried at -30℃ for 5 hours to obtain insect-repellent and environmentally friendly microcapsules.

[0116] The insect-repellent and environmentally friendly microcapsules prepared by S7 and dodecyl dimethyl betaine were stirred and mixed at 300 rpm for 3 hours at room temperature to obtain an insect-repellent and environmentally friendly asphalt additive. The mass ratio of the insect-repellent and environmentally friendly microcapsules to dodecyl dimethyl betaine was 1:1.

[0117] Heat 100 parts of base asphalt to 143°C, add 10 parts by weight of insect-repellent environmentally friendly asphalt additive at 400 rpm, and stir for 4 hours to obtain insect-repellent environmentally friendly asphalt.

[0118] Comparative Example 3

[0119] Preparation of insect-repellent and environmentally friendly microcapsules:

[0120] S1: Add tourmaline powder with a particle size of 50nm, hexadecyltrimethylammonium bromide (CTAB), and formamide to the first container. The mass ratio of tourmaline powder, hexadecyltrimethylammonium bromide (CTAB), and formamide is 1:1:30. Stir the mixture at 400 rpm for 5 hours at 160℃ to modify the surface of the nano-tourmaline powder. After the reaction is complete, wash the modified nano-tourmaline powder with ethanol several times and vacuum dry it at -30℃ for 5 hours for later use.

[0121] S2: Add bifenthrin, ethyl butyl acetaminopropionate, ethylhexyl dicycloheptendicarboximide, and camphor in equal mass ratio to the second container, and stir at 400 rpm for 5 minutes at 50°C to obtain the core material mixture.

[0122] S3: Add modified nano tourmaline powder and formamide. The mass ratio of the core material mixture, modified nano tourmaline powder and formamide is 4:1:30. Continue stirring at 400 rpm for 5 hours at 50°C.

[0123] S4: Add tetraethyl orthosilicate to the above reaction system. 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.

[0124] S5: Slowly add 10wt% dilute hydrochloric acid to the above reaction system using a peristaltic pump until the pH of the reaction system is 4. Continue stirring at 400 rpm for 5 hours at 50°C, then stop stirring and age at the same temperature for 24 hours. Then filter and wash the solid in the reaction system and vacuum dry at -30°C for 5 hours to obtain the insect-repellent and environmentally friendly microcapsule matrix.

[0125] The insect-repellent and environmentally friendly microcapsule matrix obtained in step S5 and dodecyl dimethyl betaine were stirred and mixed at 300 rpm for 3 hours at room temperature to obtain an insect-repellent and environmentally friendly asphalt additive. The mass ratio of the insect-repellent and environmentally friendly microcapsule matrix to dodecyl dimethyl betaine was 1:1.

[0126] Heat 100 parts of base asphalt to 143°C, add 10 parts by weight of insect-repellent environmentally friendly asphalt additive at 400 rpm, and stir for 4 hours to obtain insect-repellent environmentally friendly asphalt.

[0127] Test case

[0128] The frequency of insect activity in the experimental area was summarized, and the data are shown in Table 1 below.

[0129] Table 1. Frequency of insect occurrence

[0130]

[0131]

[0132] The gases released by asphalt pavement under high temperature are mainly volatile organic compounds and sulfides. To verify the smoke suppression ability of the insect-repellent and environmentally friendly asphalt composition described in this invention, samples prepared using the examples and comparative proportions were used to mix asphalt mixtures and make test blocks. The asphalt mixture test blocks were 10cm*10cm*3cm in size. The samples were then transferred into a sealed container with a gas extraction port and stored at 80°C for 2 days. After storage, the gas in the sealed container was extracted, and the VOCs and H2S contents in the gas were tested using a VOC detector and a flue gas detector. The data obtained are shown in Table 2 below.

[0133] Table 2 Asphalt Fume Test Data

[0134] Test sample FID test value / ppm <![CDATA[H2S test value / ppm]]> Base asphalt 89.8 42.6 Example 1 48.9 19.3 Example 2 49.0 19.3 Example 3 52.4 21.3 Example 4 49.1 19.4 Example 5 51.9 20.9 Example 6 50.4 20.1 Comparative Example 1 89.7 42.6 Comparative Example 2 81.3 34.4 Comparative Example 3 74.2 31.0

[0135] It should be emphasized that the above-mentioned contents are only preferred embodiments of the present invention, and should not be construed as the present invention being limited to the above description in specific implementation. For researchers and those skilled in the art to which this invention pertains, any simple deductions and improvements made without departing from the spirit and principles of the present invention should be considered within the scope of protection of the present invention.

Claims

1. An insect-repellent and environmentally friendly microcapsule, characterized in that: The shell material of the insect-repellent and environmentally friendly microcapsule is a composite shell material including silica / nano tourmaline, and the core material includes one or more of pyrethroid compounds, carboxylic acid ester compounds, amide compounds, and plant extracts; the surface of the shell material is loaded with a metal chelate, wherein the metal is copper; the chelating agent of the metal chelate is at least one of iminodiacetic acid, triethylenediamine, and hypotriacetic acid. In the composite shell, the mass ratio of silicon dioxide to nano-tourmaline is (1-5):1; The insect-repellent and environmentally friendly microcapsules are prepared using the following method: S1: Mix nano-tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze dry to obtain modified nano-tourmaline powder; S2: Mix one or more of the following: pyrethroids, lipids, amides, and plant extracts to obtain a core material mixture. S3: Add solvent and modified nano-tourmaline powder obtained in step S1 to the core material mixture obtained in step S2, and stir to mix; S4: Add the shell material precursor to the reaction system of step S3, stir and mix to obtain Pickering emulsion; S5: Adjust the pH of the Pickering emulsion obtained in step S4 to 3-6, continue stirring, then age, filter, freeze dry, and obtain the insect-repellent and environmentally friendly microcapsule matrix; S6: Disperse the insect-repellent and environmentally friendly microcapsule matrix obtained in step S5 in a methanol dispersion, then add a coupling agent methanol solution, adjust the pH of the reaction system to 9-11, process under stirring, then filter, wash, and freeze dry. S7: Disperse the solid powder obtained after freeze-drying in step S6 in a buffer solution, add a chelating agent, process under stirring, filter, wash, and freeze-dry. S8: Disperse the solid powder obtained after freeze-drying in step S7 in a metal ion salt-formamide solution, and process it under stirring. After the reaction is complete, filter, wash, and freeze-dry to obtain insect-repellent and environmentally friendly microcapsules.

2. The insect-repellent and environmentally friendly microcapsule according to claim 1, characterized in that: The diameter of the insect-repellent and environmentally friendly microcapsules is 1-3 μm.

3. The insect-repellent and environmentally friendly microcapsule according to claim 1, characterized in that: The mass ratio of the shell material to the core material of the insect-repellent and environmentally friendly microcapsule is 1:(0.8-2.0).

4. The insect-repellent and environmentally friendly microcapsule according to claim 1, characterized in that: The pyrethroid compounds have >18 carbon atoms; And / or, the number of carbon atoms in the carboxylic acid ester is >9; And / or, the amide compound has >10 carbon atoms; And / or, the plant extract has >9 carbon atoms.

5. The insect-repellent and environmentally friendly microcapsule according to claim 4, characterized in that: The pyrethroid compound is one or more of the following: cypermethrin, bifenthrin, deltamethrin, cypermethrin, ethionyl cyanide, deltamethrin, and methamidophos. And / or, the carboxylic acid ester is one or more of ethyl butyl acetaminopropionate, hexyl diethylcarbamoyl carboxylate, butyl 3-methylquinoline-4-carboxylate, dibutyl succinate, and dipropyl 2,5-pyridinedicarboxylate. And / or, the amide compound is one or more of N,N-diethyl-3-methylbenzamide, ethylhexylbicycloheptenedicarboximide, and N,N-diethylbenzamide; And / or, the plant extract is one or more of camphor and borneol.

6. The insect-repellent and environmentally friendly microcapsule according to claim 1, characterized in that: The chelating agent for the metal chelation is iminodiacetic acid; And / or: The shell material surface is loaded with metal chelates, and the metal loading accounts for 0.1wt%-10wt% of the total mass of the insect repellent and environmentally friendly microcapsules.

7. A method for preparing an insect-repellent and environmentally friendly microcapsule, characterized in that: Includes the following steps: S1: Mix nano-tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze dry to obtain modified nano-tourmaline powder; S2: Mix one or more of the following: pyrethroids, lipids, amides, and plant extracts to obtain a core material mixture. S3: Add solvent and modified nano-tourmaline powder obtained in step S1 to the core material mixture obtained in step S2, and stir to mix; S4: Add the shell material precursor to the reaction system of step S3, stir and mix to obtain Pickering emulsion; S5: Adjust the pH of the Pickering emulsion obtained in step S4 to 3-6, continue stirring, then age, filter, freeze dry, and obtain the insect-repellent and environmentally friendly microcapsule matrix; S6: Disperse the insect-repellent and environmentally friendly microcapsule matrix obtained in step S5 in a methanol dispersion, then add a coupling agent methanol solution, adjust the pH of the reaction system to 9-11, process under stirring, then filter, wash, and freeze dry. S7: Disperse the solid powder obtained after freeze-drying in step S6 in a buffer solution, add a chelating agent, process under stirring, filter, wash, and freeze-dry. S8: Disperse the solid powder obtained after freeze-drying in step S7 in a metal ion salt-formamide solution, and process it under stirring. After the reaction is complete, filter, wash, and freeze-dry to obtain insect-repellent and environmentally friendly microcapsules.

8. The method according to claim 7, characterized in that: In step S1, the surfactant is a cationic surfactant, and the solvent is an aprotic solvent with a boiling point >100℃; And / or, the mass ratio of the nano-tourmaline powder to the surfactant is (1-10):1; the mass ratio of the solvent to the surfactant is (20-40):

1.

9. The method according to claim 8, characterized in that: In step S1, the surfactant is at least one of hexadecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride; the solvent is at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide.

10. The method according to claim 8, characterized in that: In step S1, the surfactant is hexadecyltrimethylammonium bromide.

11. The method according to claim 7, characterized in that: In step S1, the stirring speed is 400-600 rpm, the modification temperature is 100-200℃, and the modification time is 4-8 hours. And / or, in step S2, the stirring speed is 400-600 rpm, the stirring temperature is 40-60°C, and the stirring time is 3-10 minutes; And / or, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60°C, and the stirring time is 4-6 hours; And / or, in step S4, the stirring speed is 400-600 rpm, the stirring temperature is 40-60°C, and the stirring time is 4-6 hours; And / or, in step S5, the stirring speed is 400-600 rpm, the stirring temperature is 40-60°C, and the stirring time is 4-6 hours; And / or, in step S6, the stirring speed is 200-450 rpm; the processing temperature is 40-60°C; and the processing time is 4-6 hours. And / or, in step S7, the stirring speed is 200-450 rpm, the processing temperature is 40-60°C, and the processing time is 2-5 hours; And / or, in step S8, the stirring speed is 200-450 rpm, the processing temperature is 100-180℃, and the processing time is 2-5 hours.

12. The method according to claim 7, characterized in that: In step S3, the solvent is an aprotic solvent with a boiling point >100℃.

13. The method according to claim 12, characterized in that: In step S3, the solvent is at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide.

14. The method according to claim 12, characterized in that: In step S3, the solvent is formamide.

15. The method according to claim 7, characterized in that: In step S3, the mass ratio of the core material mixture to the modified nano-tourmaline powder is (1-10):1; the mass ratio of the solvent to the modified nano-tourmaline powder is (20-40):

1.

16. The method according to claim 7, characterized in that: In step S4, the shell material precursor is a silicate compound; And / or, the mass ratio of the core material mixture to the shell material precursor is (0.5-2):

1.

17. The method according to claim 16, characterized in that: In step S4, the shell material precursor is at least one of methyl silicate, ethyl orthosilicate, tetraethyl orthosilicate, and butyl orthosilicate.

18. The method according to claim 7, characterized in that: In step S6, the coupling agent is a silane coupling agent.

19. The method according to claim 18, characterized in that: In step S6, the coupling agent is at least one of 3-chloropropyltrimethylsilane, (dichloromethyl)trimethylsilane, (trichloromethyl)trimethylsilane, and (chlorodifluoromethyl)trimethylsilane.

20. The method according to claim 7, characterized in that: In step S6, the mass ratio of the methanol dispersion to the insect repellent and environmentally friendly microcapsule matrix is ​​(10-20):1; the mass ratio of the insect repellent and environmentally friendly microcapsule matrix to the coupling agent methanol solution is (1-15):

1.

21. The method according to claim 7, characterized in that: The buffer solution mentioned in step S7 is one of phosphate buffer and carbonate buffer, and the pH value of the buffer solution is 9-11; And / or, in step S7, the mass ratio of the buffer solution to the solid powder obtained after lyophilization in step S6 is (15-20):

1.

22. The method according to claim 21, characterized in that: The buffer solution mentioned in step S7 is a carbonate buffer solution.

23. The method according to claim 7, characterized in that: In step S7, the ligand teeth of the chelating agent are greater than 2; And / or, in step S7, the mass ratio of the solid powder obtained after freeze-drying in step S6 to the chelating agent is (10-15):

1.

24. The method according to claim 23, characterized in that: In step S7, the chelating agent is iminodiacetic acid, triethylenediamine, or hypotriacetic acid.

25. The method according to claim 23, characterized in that: In step S7, the chelating agent is iminodiacetic acid.

26. The method according to claim 7, characterized in that: In step S8, the metal ion salt is anhydrous copper sulfate; in the metal ion salt-formamide solution, the mass ratio of the metal ion salt to formamide is (0.5-1.5):1; the mass ratio of the metal ion salt-formamide solution to the solid powder obtained after drying in step S7 is (5-15):

1.

27. An insect-repellent and environmentally friendly asphalt additive, characterized in that: It includes the following components by weight: 1-10 parts of the insect-repellent and environmentally friendly microcapsules according to any one of claims 1-6 or the insect-repellent and environmentally friendly microcapsules prepared by any one of claims 7-26; Dispersant, 1-10 parts.

28. The insect-repellent and environmentally friendly asphalt additive according to claim 27, characterized in that: The dispersant is one of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

29. An insect-repellent and environmentally friendly asphalt, characterized in that: It includes the following components by weight: Base bitumen, 100-300 parts; The insect-repellent and environmentally friendly asphalt additive according to any one of claims 27-28, 1-50 parts.

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