Smoke suppression and bird repelling microcapsule, smoke suppression and bird repelling asphalt additive and preparation method thereof

Abstract

The invention discloses a smoke-suppressing and bird-repelling microcapsule, a smoke-suppressing and bird-repelling asphalt additive and a preparation method of the smoke-suppressing and bird-repelling microcapsule. According to the smoke suppression and bird repelling microcapsule, a shell material is a composite shell material comprising silicon dioxide / nano tourmaline, and a core material comprises one or more of halogenated aromatic aldehyde and amino aromatic ester; a metal chelate is loaded on the surface of the shell material. According to the invention, the smoke suppression and bird repelling microcapsules are adopted, so that not only can road birds be durably repelled, but also the content of irritant gas in asphalt smoke can be efficiently and durably reduced, and a brand new thought is provided for environment-friendly application of asphalt.

Description

Technical Field

[0001] The invention belongs to the field of special asphalt, and specifically relates to a smoke-suppressing and bird-repelling microcapsule, a smoke-suppressing and bird-repelling asphalt additive and a preparation method thereof. Background Art

[0002] The activity areas of wild birds overlap with highways, airports and other areas, which leads to frequent car-bird and plane-bird collision accidents, seriously endangering driving and flying safety.

[0003] The places where car-bird and airplane-bird collisions occur are often very close to the ground. This is because when birds are frightened and take off while foraging on the ground, they do not have time to avoid fast-moving cars and airplanes. Therefore, developing an asphalt pavement material that can effectively drive away birds can effectively avoid bird collision accidents. At the same time, there are still some problems that are contrary to environmental protection in the application of asphalt pavement. During the paving and pavement application process, it will release irritating gases that are harmful to human health due to high temperatures, making construction workers or residents around the pavement feel uncomfortable.

[0004] CN115678289A discloses an anti-shedding sulfur asphalt and its preparation method and application. By adding sulfur to the asphalt, the birds are driven away by the unique smell released by the sulfur, thereby further avoiding the occurrence of bird collision accidents. However, the asphalt product described in this method releases more harmful and irritating gases than ordinary asphalt during construction and paving. In addition, while the asphalt product drives away birds, the smell of sulfur can also make the human body feel uncomfortable.

[0005] In summary, it is very necessary to develop an asphalt material that can effectively repel birds while reducing the amount of irritating gases released by asphalt during construction and pavement application. Summary of the invention

[0006] In view of the problems existing in the prior art, the present invention provides a smoke-suppressing bird-repelling microcapsule and a smoke-suppressing bird-repelling asphalt additive. The smoke-suppressing bird-repelling microcapsule used in the present invention can not only repel birds on the road for a long time, but also effectively and permanently reduce the content of irritating gases in asphalt smoke, providing a new idea for the environmentally friendly application of asphalt.

[0007] The first aspect of the present invention provides a smoke-suppressing and bird-repelling microcapsule, wherein the shell material is a composite shell material including silica / nano-tourmaline, and the core material includes one or more of halogenated aromatic aldehydes and amino aromatic esters; and the surface of the shell material is loaded with a metal chelate.

[0008] Furthermore, the smoke suppressant and bird repellent microcapsule has a micron structure, and its diameter is 1-5 μm.

[0009] Furthermore, the mass ratio of the shell material to the core material of the smoke suppressant and bird repellent microcapsule is 1:(0.5-2.0).

[0010] Furthermore, the core material of the smoke suppressant and bird repellent microcapsule preferably includes both halogenated aromatic aldehyde and amino aromatic ester.

[0011] Furthermore, the boiling point of the halogenated aromatic aldehyde is greater than 120° C.; preferably, it is one or more of o-chlorocinnamaldehyde, m-chlorocinnamaldehyde, p-chlorocinnamaldehyde, 3-bromocinnamaldehyde, 3-chloro-2-(chloromethyl)cinnamaldehyde, 2-chloro-3-phenylacrolein, and α-bromocinnamaldehyde.

[0012] Furthermore, the amino aromatic ester has a boiling point greater than 150° C. and is preferably one or more of methyl anthranilate, ethyl 2-aminobenzoate, ethyl 2-dimethylaminobenzoate, and butyl anthranilate.

[0013] 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.

[0014] 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.

[0015] 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 smoke-suppressing and bird-repelling microcapsules.

[0016] The second aspect of the present invention provides a method for preparing smoke-suppressing and bird-repelling microcapsules, comprising the following steps:

[0017] 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;

[0018] S2: stirring and mixing one or more of the halogenated aromatic aldehyde and the amino aromatic ester to obtain a core material mixed liquid;

[0019] 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;

[0020] S4: adding the shell material precursor to the reaction system in step S3, stirring and mixing, and obtaining a Pickering emulsion;

[0021] S5: adjusting the pH value of the Pickering emulsion obtained in step S4 to 3-6, continuing stirring, then aging, filtering, and freeze-drying to obtain a smoke-inhibiting and bird-repelling microcapsule matrix;

[0022] S6: dispersing the smoke-inhibiting and bird-repelling 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;

[0023] 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;

[0024] S8: ultrasonically disperse the solid powder obtained in step S7 in a metal ion salt-formamide solution, react under stirring, and after the reaction is completed, filter, wash, and freeze-dry to obtain smoke-inhibiting and bird-repellent microcapsules.

[0025] Furthermore, in step S1, the particle size of the nano-tourmaline powder is 10-100 nm.

[0026] Furthermore, in step S1, the surfactant is a cationic surfactant, preferably at least one of cetyltrimethylammonium bromide, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride, and more preferably cetyltrimethylammonium bromide.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] Furthermore, in step S1, the freeze-drying conditions are: vacuum drying at a temperature of -40°C to -20°C for 4-8 hours.

[0031] Furthermore, in step S2, the stirring speed is 400-600 rpm, the stirring temperature is 60-90° C., and the stirring time is 3-10 minutes.

[0032] 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.

[0033] Furthermore, in step S3, the mass ratio of the core material mixture to the modified nano-tourmaline powder is (1-5):1, and the mass ratio of the solvent to the modified nano-tourmaline powder is (20-40):1.

[0034] Furthermore, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 60-90° C., and the stirring time is 4-6 hours.

[0035] 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.

[0036] 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 60-90° C., and the stirring time is 4-6 hours.

[0037] Furthermore, in step S5, the pH can be adjusted by dropping a dilute acid, such as dilute hydrochloric acid. The stirring speed is 400-600 rpm, the stirring temperature is 60-90° C., and the stirring time is 4-6 hours.

[0038] Furthermore, in step S5, the aging condition is: standing at 60-90°C for 12-30 hours. The freeze-drying condition is: vacuum drying at a temperature of -40--20°C for 4-8 hours.

[0039] Furthermore, in step S6, the smoke suppressant and bird repellent microcapsule matrix is ​​dispersed in methanol by ultrasonic dispersion.

[0040] 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.

[0041] 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.

[0042] Furthermore, in step S6, the mass ratio of the methanol dispersion to the smoke-suppressing and bird-repelling microcapsule matrix is ​​(10-20): 1. The mass ratio of the smoke-suppressing and bird-repelling microcapsule matrix to the coupling agent methanol solution is (1-15):1.

[0043] Furthermore, in step S6, the pH may be adjusted using an alkaline solution, such as aqueous ammonia.

[0044] 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.

[0045] Furthermore, in step S6, the pH may be adjusted using an alkaline solution, such as aqueous ammonia.

[0046] 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.

[0047] Furthermore, in step S6, the reaction is carried out under the protection of nitrogen or an inert gas.

[0048] Furthermore, in step S6, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8h.

[0049] 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.

[0050] Furthermore, the buffer described in step S7 is preferably one of a phosphate buffer and a carbonate buffer, and further, preferably a carbonate buffer.

[0051] Furthermore, in step S7, the pH value of the buffer solution is 9-11.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] Furthermore, in step S7, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8h.

[0057] 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.

[0058] Further, in step S8, the metal ion salt is preferably a copper ion salt, and more preferably anhydrous copper sulfate.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] Furthermore, in step S8, the freeze-drying conditions are: vacuum drying at -40°C to -20°C for 4-8h.

[0063] The third aspect of the present invention provides a smoke-suppressing and bird-repelling asphalt additive, which comprises the following raw materials in parts by weight:

[0064] 1-10 parts of the above-mentioned smoke-suppressing and bird-repelling microcapsules;

[0065] Dispersant, 1-10 parts.

[0066] Furthermore, the dispersant is one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

[0067] Furthermore, the dispersant and the smoke-suppressing and bird-repelling microcapsules are stirred and mixed at a rotation speed of 200-400 rpm at room temperature for 1-3 hours to obtain the smoke-suppressing and bird-repelling asphalt additive.

[0068] A fourth aspect of the present invention provides a smoke-suppressing and bird-repelling asphalt, which comprises the following raw materials in parts by weight:

[0069] Base asphalt, 100-300 parts;

[0070] The above-mentioned smoke suppressing and bird repelling asphalt additive is 1-50 parts.

[0071] Furthermore, the base asphalt is heated to 133-153° C., a smoke suppressant and bird repellent asphalt additive is added at a rotation speed of 200-400 rpm, and stirred for 2-4 hours to obtain the smoke suppressant and bird repellent asphalt.

[0072] Compared with the prior art, the present invention has the following advantages:

[0073] (1) The shell material of the smoke-suppressing and bird-repelling microcapsules of the present invention is a composite shell material including silica / nano-tourmaline, which has three functions. The first function is that during the preparation process, the nano-tourmaline serves as a template for the synthesis of the microcapsules, which can maintain the stability of the core material mixed liquid droplets; the second function is that during the metal ion modification of the microcapsule composite shell material, a large amount of metal ions are adsorbed onto the surface of the microcapsules by means of the negative ion field released by the nano-tourmaline under high temperature conditions, thereby effectively increasing the metal ion loading capacity of the microcapsule shell material and further improving the smoke suppression ability; the third function is that during the service of the asphalt pavement, the nano-tourmaline contained in the shell material of the smoke-suppressing and bird-repelling microcapsules will release a negative ion field, further attracting the compounds released by the asphalt pavement under the action of high temperature to the vicinity of the smoke-suppressing and bird-repelling microcapsules, while increasing the difficulty of these compounds to volatilize, and at the same time, the metal ions on the surface of the microcapsules can react with more of the above-mentioned compounds, thereby effectively reducing the impact of the irritating gases released during the service of the asphalt pavement on the human body.

[0074] (2) The smoke-suppressing and bird-repelling asphalt of the present invention contains smoke-suppressing and bird-repelling ring microcapsules, whose shell materials are modified with a layer of chelated metal ions through surface modification technology. The 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 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 smoke.

[0075] (3) Compared with the defect of traditional smoke-suppressing and bird-repelling asphalt materials having a strong irritating odor, the smoke-suppressing and bird-repelling asphalt of the present invention has smoke-suppressing and bird-repelling microcapsules added with a fragrant aroma. After being added to asphalt, it can play a role in suppressing odor during asphalt construction and service, further reducing the sensory impact of the irritating gas released by asphalt on construction workers and residents around the construction road surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 This is a scanning electron microscope photograph of the smoke-suppressing and bird-repelling microcapsules obtained in Example 1. DETAILED DESCRIPTION

[0077] The smoke-suppressing and bird-repelling 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 smoke-suppressing and bird-repelling 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 smoke suppression and bird repellent 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] The bird-repellent effect test method of the smoke-suppressing and bird-repellent asphalt of the present invention is as follows: the smoke-suppressing and bird-repellent asphalt is prepared into a mixture test block, which is placed in an open space in a park. The volume of the test block is 300mm*300mm*50mm, and the area of ​​the test area is 100m 3 , use cameras to monitor and record the test area.

[0081] 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 the embodiments. It should be noted that the base asphalt used in the following embodiments is Sinopec Donghai Brand 70 Grade A asphalt.

[0082] Example 1

[0083] Smoke-suppressing and bird-repelling microcapsules:

[0084] S1: Add tourmaline powder with a particle size of 50 nm, hexadecyltrimethylammonium bromide and formamide into the first container, the mass ratio of tourmaline powder, hexadecyltrimethylammonium bromide (CTAB) and formamide is 1:1:30, stir 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 modification, vacuum dry at -30°C for 5 hours, and set aside;

[0085] S2: adding m-chlorocinnamaldehyde, 2-chloro-3-phenylacrolein, ethyl 2-aminobenzoate and ethyl 2-dimethylaminobenzoate in equal mass ratios into the second container, and stirring at 400 rpm for 5 minutes at 65° C. to obtain a core material mixture;

[0086] 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 65°C and 400 rpm for 5 hours;

[0087] 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 65° C. for 5 hours to obtain a Pickering emulsion;

[0088] S5: Use a peristaltic pump to slowly add 10 wt % dilute hydrochloric acid to the reaction system until the pH of the reaction system is 4, continue stirring at 400 rpm at 65° 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 a smoke-inhibiting and bird-repelling microcapsule matrix;

[0089] S6: ultrasonically disperse the smoke-inhibiting and bird-repellent microcapsule matrix obtained in step S5 in methanol, then drop 10wt% 3-chloropropyltrimethylsilane methanol solution, adjust the pH value to 11 with ammonia water, stir for 5 hours at 400 rpm and 60°C, the mass ratio of methanol, smoke-inhibiting and bird-repellent 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, filter the solid powder, wash it, and vacuum dry it at -30°C for 5 hours;

[0090] 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 at 400 rpm and 50°C for 5 hours, filter the solid powder after stirring, wash it, and vacuum dry it at -30°C for 5 hours;

[0091] S8: Ultrasonic dispersion of the solid powder obtained in S7 in a 50wt% anhydrous copper sulfate-formamide solution, with the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution being 1:10, and stirring 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 smoke-inhibiting and bird-repelling microcapsules, as shown in the electron microscope image. Figure 1 .

[0092] The smoke suppressant and bird repellent 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 a smoke suppressant and bird repellent asphalt additive. The mass ratio of the smoke suppressant and bird repellent microcapsules to dodecyl dimethyl betaine is 3:2.

[0093] Heat 100 parts of base asphalt to 143°C, add 20 parts of smoke suppressant and bird repellent asphalt additive at a rotation speed of 400 rpm, and stir for 4 hours to obtain smoke suppressant and bird repellent asphalt.

[0094] Example 2

[0095] The process is the same as in Example 1 except that step S2 is changed to adding α-bromocinnamaldehyde, 2-chloro-3-phenylacrolein, methyl anthranilate and butyl anthranilate in equal mass ratio into the second container.

[0096] Example 3

[0097] The only difference is that when preparing the smoke suppressant and bird repellent asphalt, the added amount of the smoke suppressant and bird repellent asphalt additive is 15 parts by mass, and the rest is the same as Example 1.

[0098] Example 4

[0099] The only difference is that when preparing the smoke suppression and bird repellent asphalt additive, the dispersant is changed to 1-hydroxyethyl-carboxymethyl-alkyl imidazoline, and the rest is the same as Example 1.

[0100] Example 5

[0101] 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.

[0102] Example 6

[0103] Except that the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution in step S8 is 1:7, the rest is the same as that in Example 1.

[0104] Comparative Example 1

[0105] 100 parts of base asphalt were heated to 143° C., 8 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.

[0106] Comparative Example 2

[0107] S1: adding m-chlorocinnamaldehyde, 2-chloro-3-phenylacrolein, ethyl 2-aminobenzoate and ethyl 2-dimethylaminobenzoate in equal mass ratios into the first container, and stirring at 400 rpm for 5 minutes at 65° C. to obtain a core material mixed solution;

[0108] S2: Keeping the above reaction conditions unchanged, add hexadecyltrimethylammonium bromide and formamide, the mass ratio of the core material mixture, hexadecyltrimethylammonium bromide and formamide is 6:1:30, and stir at 400 rpm at 50°C for 5 hours;

[0109] 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 65° C. for 5 hours to obtain a Pickering emulsion;

[0110] S4: Use 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, continue stirring at 400 rpm at 65°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 a smoke-inhibiting and bird-repelling microcapsule matrix;

[0111] S5: ultrasonically disperse the smoke-inhibiting and bird-repellent microcapsule matrix obtained in step S4 in methanol, then drop 10wt% 3-chloropropyltrimethylsilane methanol solution, adjust the pH value to 11 with ammonia water, stir for 5 hours at 400 rpm and 60°C, the mass ratio of methanol, smoke-inhibiting and bird-repellent 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, filter the solid powder, wash it, and vacuum dry it at -30°C for 5 hours;

[0112] 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 at 400 rpm and 50°C for 5 hours, filter the solid powder after stirring, wash it, and vacuum dry it at -30°C for 5 hours;

[0113] S7: Ultrasonic disperse the solid powder prepared 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 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 smoke suppressant and bird repellent microcapsules.

[0114] The smoke-repellent bird-repellent microcapsules prepared in step S7 and dodecyl dimethyl betaine were stirred and mixed at a rotation speed of 300 rpm at room temperature for 3 hours to prepare a smoke-repellent bird-repellent asphalt additive, and the mass ratio of the solid powder to dodecyl dimethyl betaine was 3:2.

[0115] Heat 100 parts of base asphalt to 143°C, add 20 parts of smoke suppressant and bird repellent asphalt additive at a rotation speed of 400 rpm, and stir for 4 hours to obtain smoke suppressant and bird repellent asphalt.

[0116] Comparative Example 3

[0117] S1: Add tourmaline powder with a particle size of 50 nm, hexadecyltrimethylammonium bromide and formamide into the first container, the mass ratio of tourmaline powder, hexadecyltrimethylammonium bromide (CTAB) and formamide is 1:1:30, stir 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 modification, vacuum dry at -30°C for 5 hours, and set aside;

[0118] S2: adding m-chlorocinnamaldehyde, 2-chloro-3-phenylacrolein, ethyl 2-aminobenzoate and ethyl 2-dimethylaminobenzoate in equal mass ratios into the second container, and stirring at 400 rpm for 5 minutes at 65° C. to obtain a core material mixture;

[0119] 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 65°C and 400 rpm for 5 hours;

[0120] 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 65° C. for 5 hours to obtain a Pickering emulsion;

[0121] S5: Use a peristaltic pump to slowly add 10 wt % dilute hydrochloric acid to the reaction system until the pH of the reaction system is 4, continue stirring at 400 rpm at 65° 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 a smoke-inhibiting and bird-repelling microcapsule matrix;

[0122] The smoke suppressant and bird repellent microcapsule matrix prepared by S5 and dodecyl dimethyl betaine were stirred and mixed at a rotation speed of 300 rpm at room temperature for 3 hours to prepare a smoke suppressant and bird repellent asphalt additive. The mass ratio of the smoke suppressant and bird repellent microcapsule matrix to dodecyl dimethyl betaine was 3:2.

[0123] Heat 100 parts of base asphalt to 143°C, add 20 parts of smoke suppressant and bird repellent asphalt additive at a rotation speed of 400 rpm, and stir for 4 hours to obtain smoke suppressant and bird repellent asphalt.

[0124] Test Case

[0125] The frequency of bird activities in the experimental area was summarized, and the data obtained are shown in Table 1 below.

[0126] Table 1 Frequency of bird occurrence

[0127]

[0128]

[0129] 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 smoke suppression and bird repellent asphalt additive of the present invention on asphalt materials, the samples prepared in the embodiments and comparative examples are sprinkled on the surface of the asphalt mixture test block. The size of the asphalt mixture test block is 10cm*10cm*3cm. The samples are 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 contents in the gas are tested using a VOC detector and a smoke detector. The obtained data are shown in Table 2 below.

[0130] Table 2 Asphalt smoke test data

[0131]

[0132]

[0133] It should be emphasized that the above-mentioned contents are only 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. A smoke-suppressing and bird-repelling microcapsule, characterized in that: The shell material of the smoke-suppressing and bird-repelling microcapsules is a composite shell material comprising silicon dioxide / nano-tourmaline, and the core material comprises one or more of halogenated aromatic aldehydes and amino aromatic esters; the surface of the shell material is loaded with metal chelates.

2. The smoke-suppressing and bird-repelling microcapsule according to claim 1, characterized in that: The smoke-suppressing and bird-repelling microcapsules have a micron structure, and a diameter thereof is 1-5 μm.

3. The smoke-suppressing and bird-repelling microcapsule according to claim 1, characterized in that: The mass ratio of the shell material to the core material of the smoke-suppressing and bird-repelling microcapsule is 1:(0.5-2.0).

4. The smoke-suppressing and bird-repelling microcapsule according to claim 1, characterized in that: The halogenated aromatic aldehyde has a boiling point greater than 120° C. and is preferably one or more of o-chlorocinnamaldehyde, m-chlorocinnamaldehyde, p-chlorocinnamaldehyde, 3-bromocinnamaldehyde, 3-chloro-2-(chloromethyl)cinnamaldehyde, 2-chloro-3-phenylacrolein, and α-bromocinnamaldehyde; And / or, the amino aromatic ester has a boiling point greater than 150° C.; preferably, it is one or more of methyl anthranilate, ethyl 2-aminobenzoate, ethyl 2-dimethylaminobenzoate, and butyl anthranilate.

5. The smoke-suppressing and bird-repelling 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 smoke-suppressing and bird-repelling 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 chelating agent for the metal chelate is preferably at least one of iminodiacetic acid, triethylenediamine, and nitrilotriacetic 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 smoke-suppressing and bird-repelling microcapsules.

7. A method for preparing smoke-suppressing and bird-repelling microcapsules, 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 halogenated aromatic aldehyde and the amino aromatic ester 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 a smoke-inhibiting and bird-repelling microcapsule matrix; S6: dispersing the smoke-inhibiting and bird-repelling 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: ultrasonically disperse the solid powder obtained in step S7 in a metal ion salt-formamide solution, react under stirring, and after the reaction is completed, filter, wash, and freeze-dry to obtain smoke-inhibiting and bird-repellent microcapsules.

8. The preparation 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; 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, and the mass ratio of the solvent to the surfactant is (20-40):

1.

9. The preparation 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 60-90° 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 60-90° 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 60-90° 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 60-90° 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 preparation 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.

11. The preparation 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 (1-5):1, and the mass ratio of the solvent to the modified nano-tourmaline powder is (20-40):

1.

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

1.

15. The preparation method according to claim 7, characterized in that: The buffer in step S7 is preferably one of a phosphate buffer and a carbonate buffer, and further preferably a carbonate buffer; 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 preparation 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 preparation 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. A smoke-suppressing and bird-repelling asphalt additive, characterized in that: The following raw materials are included by weight: 1-10 parts of the smoke-suppressing and bird-repelling microcapsules according to any one of claims 1-6 or the smoke-suppressing and bird-repelling microcapsules prepared by the method according to any one of claims 7-17; Dispersant, 1-10 parts.

19. The smoke-suppressing and bird-repelling asphalt additive according to claim 18, characterized in that: The dispersant is one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

20. A smoke-suppressing and bird-repelling asphalt, characterized in that: The following raw materials are included by weight: Base asphalt, 100-300 parts; 1-50 parts of the smoke suppressing and bird repelling asphalt additive according to any one of claims 18-19.

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