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

Abstract

The invention discloses an insect-repelling environment-friendly microcapsule, an insect-repelling environment-friendly asphalt additive and a preparation method of the insect-repelling environment-friendly microcapsule. A shell material of the insect-repelling environment-friendly microcapsule is a composite shell material containing silicon dioxide / nano tourmaline, and a core material of the insect-repelling environment-friendly microcapsule comprises one or more of a pyrethroid compound, a carboxylic ester compound, an amide compound and a plant extract; a metal chelate is loaded on the surface of the shell material. The insect-repelling environment-friendly microcapsule disclosed by the invention not only can efficiently and durably repel insects around a road, but also can effectively inhibit the amount of pollutants generated by the asphalt under the action of high temperature in the production, construction and pavement application processes, and provides a brand new idea for functional utilization of asphalt materials.

Description

Technical Field

[0001] The invention belongs to the field of special asphalt, and specifically relates to an insect repellent and environmentally friendly microcapsule, an insect repellent and environmentally friendly asphalt additive and a preparation method thereof. Background Art

[0002] With the rapid development of China's road engineering, the total mileage of China's expressways has reached the forefront of the world in recent years. However, there are still some problems that have not been solved in the process of putting expressways into use. First, the number of insects increases significantly in summer and autumn. The activity range of some insects covers some expressways, causing vehicles to hit a large number of insects during high-speed driving, making a large number of insect corpses that are difficult to clean adhere to the windshield of the vehicle, seriously blocking the driver's vision and endangering driving safety; second, during the hot construction and service of asphalt pavement, the high temperature will release toxic and harmful irritating gases, which will not only pollute the environment, but also affect human health and cause discomfort to the human body.

[0003] CN115678289A discloses an anti-shedding sulfur asphalt and its preparation method and application, which adds a large amount of sulfur to the asphalt so that the asphalt releases a large amount of sulfur-specific pungent smell during the road service, and the purpose of repelling insects is achieved by using the smell. However, the sulfur smell released by the asphalt product produced by this method can make people feel uncomfortable while repelling insects, and the asphalt product mentioned in this method releases more toxic and irritating gases during production, construction and road application than ordinary base asphalt, which is contrary to the green and low-carbon development strategy.

[0004] Therefore, there is an urgent need to develop a pavement material that can effectively inhibit the release of toxic asphalt gases and prevent insect pests, so as to achieve the dual goals of driving safety and environmental protection. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention provides an insect repellent environmentally friendly microcapsule, an insect repellent environmentally friendly asphalt additive and a preparation method thereof. The insect repellent environmentally friendly microcapsule of the present invention can not only efficiently and permanently drive away insects around roads, but also effectively inhibit the amount of pollutants generated by high temperature during the production, construction and road surface use of asphalt, providing a new idea for 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 including silica / nano-tourmaline, and the core material includes one or more of pyrethroid compounds, carboxylic acid ester compounds, amide compounds, and plant extracts; and the surface of the shell material is loaded with a metal chelate.

[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 at the same time.

[0010] Furthermore, the pyrethroid compound has a carbon number greater than 18; preferably, it is one or more of cypermethrin, bifenthrin, flumethrin, cypermethrin, acepromazine, deltamethrin, and tetramethrin.

[0011] Furthermore, the carbon number of the carboxylic acid ester is greater than 9; preferably, it is one or more of ethyl butyl acetylaminopropionate, hexyl diethylcarbamoylformate, butyl 3-methylquinoline-4-carboxylate, dibutyl succinate, and dipropyl 2,5-pyridinedicarboxylate.

[0012] Furthermore, the carbon number of the amide compound is greater than 10; preferably, it is one or more of N,N-diethyl-3-methylbenzamide, ethylhexyl bicycloheptene dicarboximide, and N,N-diethylbenzamide.

[0013] Furthermore, the carbon number of the plant extract is greater than 9; preferably, it is 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 metal chelating agent is preferably at least one of iminodiacetic acid, triethylenediamine, and nitrilotriacetic acid, and more preferably iminodiacetic acid.

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

[0017] The second aspect of the present invention provides a method for preparing insect repellent environmentally friendly microcapsules, comprising the following steps:

[0018] S1: mixing nano tourmaline powder, a surfactant and a solvent, modifying the mixture under stirring, washing the mixture after modification, and freeze-drying the mixture to obtain modified nano tourmaline powder;

[0019] S2: stirring and mixing one or more of the pyrethroid compound, lipid compound, amide compound, and plant extract to obtain a core material mixed liquid;

[0020] S3: adding the solvent and the modified nano-tourmaline powder obtained in step S1 to the core material mixed solution obtained in step S2, and stirring and mixing;

[0021] S4: adding the shell material precursor to the reaction system in step S3, stirring and mixing, and obtaining a Pickering emulsion;

[0022] S5: adjusting the pH value of the Pickering emulsion obtained in step S4 to 3-6, continuing stirring, and then aging, filtering, and freeze-drying to obtain an insect repellent and environmentally friendly microcapsule matrix;

[0023] S6: dispersing the insect repellent and environmentally friendly microcapsule matrix obtained in step S5 in a methanol dispersion, then adding a coupling agent methanol solution, and adjusting the pH value of the reaction system to 9-11, treating under stirring, and then filtering, washing, and freeze-drying;

[0024] S7: dispersing the solid powder obtained after freeze-drying in step S6 in a buffer, adding a chelating agent, treating under stirring, filtering, washing, and freeze-drying;

[0025] S8: dispersing the solid powder obtained after freeze-drying in step S7 in a metal ion salt-formamide solution, treating under stirring, filtering, washing, and freeze-drying after the reaction is completed, 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] Furthermore, in step S1, the surfactant is a cationic surfactant, preferably at least one of cetyltrimethylammonium bromide (CTAB), dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride, and more preferably cetyltrimethylammonium bromide (CTAB).

[0028] Furthermore, in step S1, the solvent is an aprotic solvent with a boiling point > 100°C, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0029] Furthermore, 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] Furthermore, in step S1, the stirring speed is 400-600 rpm; the modification temperature is 100-200° C., and the modification time is 4-8 hours.

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

[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] Furthermore, in step S3, the solvent is an aprotic solvent with a boiling point > 100°C, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0034] Furthermore, 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° C., and the stirring time is 4-6 hours.

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

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

[0038] Furthermore, in step S5, the pH value can be adjusted by using dilute acid, such as dilute hydrochloric acid. The stirring speed is 400-600 rpm, the stirring temperature is 40-60° C., and the stirring time is 4-6 hours.

[0039] Furthermore, in step S5, the aging condition is: standing at 40-60°C for 12-30 hours. The freeze-drying condition is: vacuum drying at a temperature of -40--20°C for 4-8 hours.

[0040] Furthermore, in step S6, the insect repellent and environmentally friendly microcapsule matrix is ​​dispersed in methanol 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, (chlorodifluoromethyl)trimethylsilane, and more preferably 3-chloropropyltrimethylsilane.

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

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

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

[0045] Furthermore, in step S6, the stirring speed is 200-450 rpm; the treatment temperature is 40-60° C., and the treatment 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 4-8h.

[0048] Furthermore, in step S7, the solid powder obtained after freeze-drying in step S6 is dispersed in a buffer solution, and ultrasonic dispersion can be used.

[0049] Furthermore, the buffer described in step S7 is preferably one of a phosphate buffer and a carbonate buffer, and further, preferably a carbonate buffer.

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

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

[0052] Furthermore, in step S7, the ligand tooth number of the chelating agent is greater than 2, and is preferably iminodiacetic acid, triethylenediamine, or nitrilotriacetic acid, and more preferably iminodiacetic acid.

[0053] Furthermore, 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 treatment temperature is 40-60° C., and the treatment time is 2-5 hours.

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

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

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

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

[0059] Furthermore, 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 treatment temperature is 100-180° C., and the treatment time is 2-5 hours.

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

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

[0063] 1-10 parts of the above-mentioned environmentally friendly insect repellent microcapsules;

[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 environmentally friendly microcapsules are stirred and mixed at a rotation speed of 200-400 rpm at room temperature for 1-3 hours to obtain the insect repellent 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 asphalt, 100-300 parts;

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

[0070] Furthermore, the base asphalt is heated to 133-153° C., the insect repellent and environment-friendly asphalt additive is added at a rotation speed of 200-400 rpm, and stirred for 2-4 hours to obtain the insect repellent and environment-friendly asphalt.

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

[0072] (1) The shell material of the insect repellent environmentally friendly microcapsules of the present invention is a composite shell material including silica / nano-tourmaline, wherein in the process of preparing the insect repellent environmentally friendly microcapsules, tourmaline powder can replace the template agent for microcapsule synthesis to maintain the stability of the microcapsule core material droplets; in addition, in the process of metal ion modification of the shell material, a large amount of metal ions can be adsorbed onto the surface of the microcapsule with the help of the negative ion field released by the tourmaline, effectively increasing the loading capacity of the transition metal ions of the microcapsule shell material, and can react chemically with the sulfide released by the asphalt pavement under high temperature, effectively reducing the malodorous gas released by the asphalt under high temperature and sunlight, and avoiding the discomfort caused by the asphalt pavement to the human body; further, in the process of pavement service, after the insect repellent environmentally friendly microcapsules are heated, the nano-tourmaline powder contained in 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 environmentally friendly microcapsules, while increasing the difficulty of these compounds to volatilize, the metal ions on the surface of the microcapsule can react with more of the above-mentioned compounds, further inhibiting their volatilization, thereby effectively reducing the impact of the irritating gas released by the asphalt pavement on the human body.

[0073] (2) The insect repellent environmentally friendly asphalt of the present invention contains insect repellent environmentally friendly microcapsules, whose shell materials are modified with a layer of chelated metal ions through surface modification technology. This layer of chelated metal ions has empty orbits. After the microcapsules enter the asphalt system, the chelated metal ions can directly accept the unshared electrons of some relatively active sulfur-containing and nitrogen-containing pollutants in the asphalt and form coordination bonds, thereby stably fixing the above-mentioned compounds on the surface of the microcapsules, avoiding their high-temperature volatilization, and further quickly reducing the content of irritating gases in the asphalt fume;

[0074] (3) The insect repellent and environmentally friendly asphalt of the present invention contains insect repellent and environmentally friendly microcapsules, and the insect repellent components with lower boiling points are coated in a silica / nano-tourmaline composite shell material. These active components can be slowly released from the microcapsules during the application of asphalt pavement, so that insects are kept away from the pavement area, avoiding the impact of insects on pedestrian and driving safety, and have a long-lasting insect repellent effect, which can avoid repeated construction. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 This is a scanning electron microscope photo of the insect repellent and environmentally friendly microcapsules obtained in Example 1. DETAILED DESCRIPTION

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

[0077] The insect repellent and environmentally friendly microcapsules of the present invention are tested for morphology by scanning electron microscopy, and the acceleration voltage used is 20KV. Since the wall material of the microcapsule is not conductive, the sample needs to be treated with gold spraying before the test.

[0078] The insect repellent and environmentally friendly microcapsules of the present invention are tested for surface elements by an X-ray spectrometer to confirm that the metal ions are successfully modified on the surface of the microcapsules.

[0079] The smoke suppression effect of the insect repellent and environmentally friendly asphalt of the present invention is tested by a VOC detector with an FID detector and a smoke detector with an H2S electrochemical sensor.

[0080] In the present invention, the anthelmintic effect is evaluated by the following method:

[0081] The insect repellent environmentally friendly asphalt was prepared into a mixture test block and placed in an open space in a park. The volume of the test block was 300mm*300mm*50mm, and the test area was 100m 3 , use cameras to monitor and record the test area.

[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 environmentally friendly microcapsules:

[0085] S1: Add tourmaline powder with a particle size of 50 nm, hexadecyltrimethylammonium bromide (CTAB) and formamide into the first container, the mass ratio of tourmaline powder, hexadecyltrimethylammonium bromide (CTAB) and formamide is 1:1:30, stir and react at 160°C and 400 rpm for 5 hours to modify the surface of the nano tourmaline powder, wash the modified nano tourmaline with ethanol for multiple times after the reaction is completed, and vacuum dry for 5 hours at -30°C for standby use;

[0086] S2: adding bifenthrin, ethyl butyl acetylaminopropionate, ethylhexyl bicycloheptene dicarboximide and camphor in equal weight ratios to the second container, and stirring at 400 rpm for 5 minutes at 50° C. to obtain a core material mixed solution;

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

[0088] S4: adding tetraethyl orthosilicate to the above reaction system, with the mass ratio of the core material mixture to tetraethyl orthosilicate being 1:1, and continuing to stir at 400 rpm at 50° C. for 5 hours to obtain a Pickering emulsion;

[0089] S5: using a peristaltic pump, slowly adding 10 wt % dilute hydrochloric acid to the reaction system until the pH of the reaction system is 4, continuing to stir at 400 rpm for 5 hours at 50° C., then stopping stirring, keeping the temperature unchanged and aging for 24 hours, then filtering and washing the solid in the reaction system, and vacuum drying at -30° C. for 5 hours to obtain an insect repellent and environmentally friendly microcapsule matrix;

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

[0091] S7: ultrasonically disperse the solid powder obtained in S6 in a carbonate buffer solution of pH=11, then add iminodiacetic acid, the mass ratio of carbonate buffer solution, solid powder and iminodiacetic acid is 150:10:1, stir and react at 400 rpm and 50°C for 5 hours, filter and wash the solid powder after stirring, and vacuum dry at -30°C for 5 hours;

[0092] S8: Ultrasonic dispersion of the solid powder obtained in S7 in a 50wt% anhydrous copper sulfate-formamide solution, the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution being 1:10, stirring and reacting at 400 rpm and 140°C for 5 hours. After stirring, the solid powder is filtered, washed, and vacuum dried at -30°C for 5 hours to obtain insect repellent environmentally friendly microcapsules, as shown in the electron microscope image. Figure 1 .

[0093] The insect repellent environmentally friendly microcapsules prepared in step S8 and dodecyl dimethyl betaine are stirred and mixed at a rotation speed of 300 rpm at room temperature for 3 hours to prepare an insect repellent environmentally friendly asphalt additive, and the mass ratio of the insect repellent environmentally friendly microcapsules to dodecyl dimethyl betaine is 1:1.

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

[0095] Example 2

[0096] The process is the same as in Example 1 except that step S2 is changed to adding equal mass ratios of deltamethrin, 3-methylquinoline-4-carboxylic acid butyl ester, N,N-diethyl-3-methylbenzamide and bornyl alcohol into the second container.

[0097] Example 3

[0098] The method is the same as that in Example 1 except that the amount of the insect repellent environmentally friendly asphalt additive used is 5 parts by mass when preparing the insect repellent environmentally friendly asphalt.

[0099] Example 4

[0100] The method is the same as that in Example 1 except that the dispersant is 1-hydroxyethyl-carboxymethyl-alkyl imidazoline when preparing the insect repellent and environmentally friendly asphalt additive.

[0101] Example 5

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

[0103] Example 6

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

[0105] Comparative Example 1

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

[0107] Comparative Example 2

[0108] Preparation of insect repellent environmentally friendly microcapsules:

[0109] S1: adding bifenthrin, ethyl butyl acetylaminopropionate, ethylhexyl bicycloheptene dicarboximide and camphor in equal weight ratios to the first container, and stirring at 400 rpm for 5 minutes at 50° C. to obtain a core material mixed solution;

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

[0111] S3: adding tetraethyl orthosilicate to the above reaction system, with the mass ratio of the core material mixture to tetraethyl orthosilicate being 1:1, and continuing to stir at 400 rpm at 50° C. for 5 hours to obtain a Pickering emulsion;

[0112] S4: using a peristaltic pump to slowly drop 10 wt % dilute hydrochloric acid into the above reaction system until the pH of the reaction system is 4, stirring is continued at 400 rpm for 5 hours at 50° C., and then the stirring is stopped, and the temperature is kept unchanged for aging for 24 hours, and then the solid in the reaction system is filtered and washed, and vacuum dried at -30° C. for 5 hours to obtain an insect repellent environmentally friendly microcapsule matrix;

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

[0114] S6: ultrasonically disperse the solid powder obtained in S5 in a carbonate buffer solution of pH=11, then add iminodiacetic acid, the mass ratio of carbonate buffer solution, solid powder and iminodiacetic acid is 150:10:1, stir and react at 400 rpm and 50°C for 5 hours, filter and wash the solid powder after stirring, and vacuum dry at -30°C for 5 hours;

[0115] S7: Ultrasonic disperse the solid powder obtained in S6 in 50wt% anhydrous copper sulfate-formamide solution, the mass ratio of solid powder to anhydrous copper sulfate-formamide solution is 1:10, stir and react at 400 rpm and 140°C for 5 hours, filter and wash the solid powder after stirring, and vacuum dry it at -30°C for 5 hours to obtain insect repellent environmentally friendly microcapsules.

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

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

[0118] Comparative Example 3

[0119] Preparation of insect repellent environmentally friendly microcapsules:

[0120] S1: Add tourmaline powder with a particle size of 50 nm, hexadecyltrimethylammonium bromide (CTAB) and formamide into the first container, the mass ratio of tourmaline powder, hexadecyltrimethylammonium bromide (CTAB) and formamide is 1:1:30, stir and react at 160°C and 400 rpm for 5 hours to modify the surface of the nano tourmaline powder, wash the modified nano tourmaline with ethanol for multiple times after the reaction is completed, and vacuum dry for 5 hours at -30°C for standby use;

[0121] S2: adding bifenthrin, ethyl butyl acetylaminopropionate, ethylhexyl bicycloheptene dicarboximide and camphor in equal weight ratios to the second container, and stirring at 400 rpm for 5 minutes at 50° C. to obtain a core material mixed solution;

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

[0123] S4: adding tetraethyl orthosilicate to the above reaction system, with the mass ratio of the core material mixture to tetraethyl orthosilicate being 1:1, and continuing to stir at 400 rpm at 50° C. for 5 hours to obtain a Pickering emulsion;

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

[0125] The insect repellent environmentally friendly microcapsule matrix prepared in step S5 and dodecyl dimethyl betaine are stirred and mixed at a rotation speed of 300 rpm at room temperature for 3 hours to prepare an insect repellent environmentally friendly asphalt additive, and the mass ratio of the insect repellent environmentally friendly microcapsule matrix to dodecyl dimethyl betaine is 1:1.

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

[0127] Test Case

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

[0129] Table 1 Frequency of insect occurrence

[0130]

[0131]

[0132] The gases released by asphalt pavement under the influence of high temperature are mainly volatile organic compounds and sulfides. In order to verify the smoke suppression ability of the insect repellent and environmentally friendly asphalt composition of the present invention, the samples prepared in the embodiments and comparative examples are used to mix the asphalt mixture and make test blocks. The size of the asphalt mixture test block is 10cm*10cm*3cm. The sample is further moved into a sealed container with a gas intake port and stored at a temperature of 80°C for 2 days. After the storage is completed, the gas in the sealed container is absorbed, and the VOCs and H2S content in the gas are tested using a VOC detector and a smoke detector. The obtained data are shown in Table 2 below.

[0133] Table 2 Asphalt smoke test data

[0134] Test samples 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 it cannot be determined that the present invention is limited to the above description in the specific implementation process. For scientific research and technical personnel in the technical field to which the present invention belongs, any simple deduction and improvement made without departing from the ideas and principles of the present invention shall be deemed to be within the scope of protection of the present invention.

Claims

1. An environmentally friendly insect repellent microcapsule, characterized in that: The shell material of the insect repellent environmentally friendly microcapsule is a composite shell material including silicon dioxide / 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 metal chelates.

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

3. The insect repellent 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 environmentally friendly microcapsule is 1:(0.8-2.0).

4. The insect repellent environmentally friendly microcapsule according to claim 1, characterized in that: The pyrethroid compound has a carbon number of >18; preferably one or more of cypermethrin, bifenthrin, flumethrin, cypermethrin, acepromazine, deltamethrin, and tetramethrin; And / or, the carbon number of the carboxylic acid ester is greater than 9; preferably one or more of ethyl butyl acetylaminopropionate, hexyl diethylcarbamoylformate, butyl 3-methylquinoline-4-carboxylate, dibutyl succinate, and dipropyl 2,5-pyridinedicarboxylate; And / or, the carbon number of the amide compound is greater than 10; preferably one or more of N,N-diethyl-3-methylbenzamide, ethylhexyl bicycloheptene dicarboximide, and N,N-diethylbenzamide; And / or, the carbon number of the plant extract is greater than 9; preferably, it is one or more of camphor and borneol.

5. The insect repellent environmentally friendly microcapsule according to claim 1, characterized in that: The shell material is a silicon dioxide / nano-tourmaline composite shell material, wherein the mass ratio of silicon dioxide to nano-tourmaline is (1-5):

1.

6. The insect repellent environmentally friendly microcapsule according to claim 1, characterized in that: The surface of the shell material is loaded with a metal chelate, wherein the metal is preferably copper. The metal chelating agent is preferably at least one of iminodiacetic acid, triethylenediamine, and nitrilotriacetic acid, and more preferably iminodiacetic acid; And / or: the surface of the shell material is loaded with metal chelates, and the metal loading accounts for 0.1wt%-10wt% of the total mass of the insect repellent environmentally friendly microcapsules.

7. A method for preparing an insect repellent environmentally friendly microcapsule, characterized in that: The following steps are involved: S1: mixing nano tourmaline powder, a surfactant and a solvent, modifying the mixture under stirring, washing the mixture after modification, and freeze-drying the mixture to obtain modified nano tourmaline powder; S2: stirring and mixing one or more of the pyrethroid compound, lipid compound, amide compound, and plant extract to obtain a core material mixed liquid; S3: adding the solvent and the modified nano-tourmaline powder obtained in step S1 to the core material mixed solution obtained in step S2, and stirring and mixing; S4: adding the shell material precursor to the reaction system in step S3, stirring and mixing, and obtaining a Pickering emulsion; S5: adjusting the pH value of the Pickering emulsion obtained in step S4 to 3-6, continuing stirring, and then aging, filtering, and freeze-drying to obtain an insect repellent and environmentally friendly microcapsule matrix; S6: dispersing the insect repellent and environmentally friendly microcapsule matrix obtained in step S5 in a methanol dispersion, then adding a coupling agent methanol solution, and adjusting the pH value of the reaction system to 9-11, treating under stirring, and then filtering, washing, and freeze-drying; S7: dispersing the solid powder obtained after freeze-drying in step S6 in a buffer, adding a chelating agent, treating under stirring, filtering, washing, and freeze-drying; S8: dispersing the solid powder obtained after freeze-drying in step S7 in a metal ion salt-formamide solution, treating under stirring, filtering, washing, and freeze-drying after the reaction is completed, 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, preferably at least one of hexadecyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride, and more preferably hexadecyltrimethylammonium bromide; the solvent is an aprotic solvent with a boiling point > 100°C, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide; 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 7, characterized in that: In step S1, the stirring speed is 400-600 rpm, the modification temperature is 100-200° C., 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 treatment temperature is 40-60° C., and the treatment time is 4-6 hours; And / or, in step S7, the stirring speed is 200-450 rpm, the treatment temperature is 40-60° C., and the treatment time is 2-5 hours; And / or, in step S8, the stirring speed is 200-450 rpm, the treatment temperature is 100-180° C., and the treatment time is 2-5 hours.

10. The method according to claim 7, characterized in that: In step S3, the solvent is an aprotic solvent with a boiling point > 100°C, preferably at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

11. 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.

12. The method according to claim 7, characterized in that: In step S4, the shell material precursor is a silicate compound, preferably at least one of methyl silicate, ethyl orthosilicate, tetraethyl orthosilicate, and butyl orthosilicate; And / or, the mass ratio of the core material mixed liquid to the shell material precursor is (0.5-2):

1.

13. The method according to claim 7, characterized in that: 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.

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

1.

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

1.

16. The method according to claim 7, characterized in that: In step S7, the ligand tooth number of the chelating agent is greater than 2, preferably iminodiacetic acid, triethylenediamine, nitrilotriacetic acid, and more preferably iminodiacetic acid; 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.

17. The method according to claim 7, characterized in that: In step S8, the metal ion salt is preferably a copper ion salt, and more preferably 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.

18. An insect repellent and environmentally friendly asphalt additive, characterized by: The following components are included by weight: 1-10 parts of the insect repellent microcapsules according to any one of claims 1-6 or the insect repellent microcapsules prepared by the method according to any one of claims 7-17; Dispersant, 1-10 parts.

19. The insect repellent and environmentally friendly asphalt additive according to claim 18, characterized in that: The dispersant is one of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

20. An insect repellent and environmentally friendly asphalt, characterized by: The following components are included by weight: Base asphalt, 100-300 parts; 1-50 parts of the insect repellent and environmentally friendly asphalt additive according to any one of claims 18-19.

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