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

Abstract

The application discloses a smoke-reducing and bird-repelling microcapsule, a smoke-reducing and bird-repelling asphalt additive and a preparation method thereof. The shell material of the smoke-reducing and bird-repelling microcapsule is a composite shell material comprising silicon dioxide / nano tourmaline, the core material comprises one or more of halogenated aromatic aldehyde and amino aromatic ester, and the surface of the shell material is loaded with a metal chelate. The smoke-reducing and bird-repelling microcapsule can not only persistently drive away road birds, but also efficiently and persistently reduce the content of irritating gases in asphalt smoke, thereby providing a brand-new idea for the environment-friendly application of asphalt.

Description

Technical Field

[0001] This invention belongs to the field of special asphalt, specifically relating to a smoke-suppressing and bird-repelling microcapsule, a smoke-suppressing and bird-repelling asphalt additive, and a method for preparing the same. Background Technology

[0002] The activity areas of wild birds overlap with those of highways and airports, which leads to frequent bird strikes by vehicles and aircraft, seriously endangering driving and flight safety.

[0003] Bird strikes involving vehicles and aircraft often occur very close to the ground because birds, startled while foraging on the ground, cannot avoid the speeding cars and planes in time to take flight. Therefore, developing an asphalt pavement material that can effectively repel birds could significantly prevent bird strikes. However, asphalt pavement also presents some environmental problems during its application. During paving and application, the high temperatures released can release irritating gases harmful to human health, causing discomfort to construction workers and residents in the vicinity.

[0004] CN115678289A discloses an anti-shedding sulfur asphalt, its preparation method, and its application. By adding sulfur to the asphalt, the characteristic odor released by sulfur repels birds, further preventing bird strikes. However, the asphalt product produced by this method releases a higher amount of harmful and irritating gases during construction and paving compared to ordinary asphalt. Furthermore, while repelling birds, the sulfur odor can also cause discomfort to humans.

[0005] In conclusion, it is essential to develop an asphalt material that can effectively repel birds while reducing the amount of irritating gases released during construction and road application. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a smoke-suppressing and bird-repelling microcapsule and a smoke-suppressing and bird-repelling asphalt additive. This invention utilizes smoke-suppressing and bird-repelling microcapsules, which not only persistently repel road birds but also efficiently and persistently reduce the content of irritating gases in asphalt fumes, providing a novel approach to 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 comprising silica / 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.

[0008] Furthermore, the smoke-suppressing and bird-repelling microcapsules have a micron structure with a diameter of 1-5 μm.

[0009] Furthermore, 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).

[0010] Furthermore, the core material of the smoke-suppressing and bird-repelling microcapsules preferably includes both halogenated aromatic aldehydes and amino aromatic esters.

[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-phenylpropenal, and α-bromocinnamaldehyde.

[0012] Furthermore, 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.

[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 chelating agent for the metal chelation is preferably at least one selected from iminodiacetic acid, triethylenediamine, and hypozinotriacetic acid, and more preferably iminodiacetic acid.

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

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

[0017] S1: Mix nano-tourmaline powder, surfactant and solvent, modify under stirring, wash after modification, freeze dry to obtain modified nano-tourmaline powder;

[0018] S2: Mix one or more of halogenated aromatic aldehydes and amino aromatic esters to obtain a core material mixture;

[0019] 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;

[0020] S4: Add the shell material precursor to the reaction system of step S3, stir and mix to obtain Pickering emulsion;

[0021] 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 smoke-suppressing and bird-repelling microcapsule matrix;

[0022] S6: Disperse the smoke-suppressing and bird-repelling microcapsule matrix obtained in step S5 in a methanol dispersion, then add a methanol solution of coupling agent, adjust the pH of the reaction system to 9-11, process under stirring, then filter, wash, and freeze dry.

[0023] 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.

[0024] S8: The solid powder obtained after drying in step S7 is ultrasonically dispersed in a metal ion salt-formamide solution and reacted under stirring. After the reaction is completed, the powder is filtered, washed, and freeze-dried to obtain smoke-suppressing and bird-repelling microcapsules.

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

[0026] Further, 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.

[0027] 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.

[0028] 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.

[0029] 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.

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

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

[0032] 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.

[0033] Further, 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℃, and the stirring time is 4-6 hours.

[0035] 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.

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

[0037] Furthermore, in step S5, pH adjustment can be achieved by adding dilute acid, such as dilute hydrochloric acid. The stirring speed is 400-600 rpm, the stirring temperature is 60-90℃, and the stirring time is 4-6 hours.

[0038] Further, in step S5, the aging conditions are: standing at 60-90℃ for 12-30 hours. The freeze-drying conditions are: vacuum drying at -40---20℃ for 4-8 hours.

[0039] Furthermore, in step S6, the smoke-suppressing and bird-repelling microcapsule matrix is ​​dispersed in methanol, which can be achieved 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, and (chlorodifluoromethyl)trimethylsilane, and more preferably 3-chloropropyltrimethylsilane.

[0041] 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.

[0042] Further, 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 can be adjusted using an alkaline solution, such as ammonia.

[0044] 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.

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

[0046] 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.

[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 4-8 hours.

[0049] Furthermore, in step S7, the solid powder obtained after lyophilization in step S6 can be dispersed in a buffer solution by ultrasonic dispersion.

[0050] Furthermore, the buffer solution mentioned in step S7 is preferably one of phosphate buffer and carbonate buffer, and more preferably carbonate buffer.

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

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

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

[0057] 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.

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

[0059] 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.

[0060] 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.

[0061] 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.

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

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

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

[0065] Dispersant, 1-10 parts.

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

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

[0068] The fourth aspect of this invention provides a smoke-suppressing and bird-repelling asphalt, comprising the following raw materials by weight:

[0069] Base bitumen, 100-300 parts;

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

[0071] Further, the base asphalt is heated to 133-153℃, and smoke-suppressing and bird-repelling asphalt additives are added at a speed of 200-400 rpm. After stirring for 2-4 hours, smoke-suppressing and bird-repelling asphalt can be obtained.

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

[0073] (1) The smoke-suppressing and bird-repelling microcapsules of the present invention have a shell material comprising a composite shell material of silica / nano-tourmaline, which has three functions. The first function is that during the preparation process, nano-tourmaline serves as a template agent for the synthesis of microcapsules, which can maintain the stability of the core material mixture droplets. The second function is that during the metal ion modification process of the microcapsule composite shell material, the negative ion field released by nano-tourmaline under high temperature conditions is used to adsorb a large number of metal ions onto the surface of the microcapsules, effectively increasing the metal ion loading of the microcapsule shell material and further enhancing the smoke-suppressing ability. The third function is that during the service of asphalt pavement, the nano-tourmaline contained inside the smoke-suppressing and bird-repelling microcapsule 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 smoke-suppressing and bird-repelling microcapsules. While increasing the difficulty of these compounds volatilizing, it can also cause the metal ions on the surface of the microcapsules to react with more of the above-mentioned compounds, thereby effectively reducing the impact of the irritating gases released during the service of 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. The shell material is modified with a layer of chelated metal ions through surface modification technology. These chelated metal ions have 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 coordination bonds, thus stably fixing the above compounds on the surface of the microcapsules, avoiding their volatilization at high temperatures, and further rapidly reducing the content of irritating gases in the asphalt fumes.

[0075] (3) Compared with the shortcomings of traditional smoke-suppressing and bird-repelling asphalt materials with strong irritating odor, the smoke-suppressing and bird-repelling asphalt of the present invention has smoke-suppressing and bird-repelling microcapsules with fragrant aroma. After being added to asphalt, it can play a role in suppressing odor during asphalt construction and service, further reducing the impact of irritating gases released by asphalt on the sensory experience of construction workers and residents around the construction road. Attached Figure Description

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

[0077] The morphology of the smoke-suppressing and bird-repelling microcapsules described in this invention was tested by scanning electron microscopy. The accelerating voltage used was 20KV. Since the microcapsule wall material is non-conductive, the sample needs to be sputtered with gold before testing.

[0078] The smoke-suppressing and bird-repelling microcapsules of the present invention were subjected to surface elemental analysis 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 smoke-suppressing and bird-repelling asphalt described in this invention was tested using a VOC detector with an FID detector and a smoke detector with an H2S electrochemical sensor.

[0080] The method for testing the bird-repelling effect of the smoke-suppressing and bird-repelling asphalt described in this invention is as follows: The smoke-suppressing and bird-repelling asphalt is prepared into a mixed test block, which is placed in an open area of ​​a park. The volume of the test block is 300mm*300mm*50mm, and the test area is 100m². 3 The test area was monitored and recorded using cameras.

[0081] To further illustrate the relevant features and technical means of the present invention, the present invention will be clearly and in detail described below with reference to the embodiments. It should be noted that the base asphalt used in the following embodiments is Sinopec Donghai brand No. 70 Grade A asphalt.

[0082] Example 1

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

[0084] 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 at 400 rpm for 5 hours at 160℃ to modify the surface of the nano-tourmaline powder. After modification, wash the modified nano-tourmaline powder with ethanol multiple times and vacuum dry at -30℃ for 5 hours for later use.

[0085] S2: Add equal mass ratios of m-chlorocinnamaldehyde, 2-chloro-3-phenylpropenal, ethyl 2-aminobenzoate, and ethyl 2-dimethylaminobenzoate to the second container, and stir at 400 rpm for 5 minutes at 65°C to obtain the core material mixture.

[0086] 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 65°C.

[0087] 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 65°C to obtain Pickering emulsion.

[0088] 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 65℃, 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℃ for 5 hours to obtain the smoke-suppressing and bird-repelling microcapsule matrix.

[0089] S6: The smoke-suppressing and bird-repelling 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 mixture was stirred for 5 hours at 400 rpm and 60°C. The mass ratio of methanol, smoke-suppressing and bird-repelling 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.

[0090] 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.

[0091] S8: The solid powder obtained in S7 was ultrasonically dispersed in a 50 wt% anhydrous copper sulfate-formamide solution, with a mass ratio of solid powder to anhydrous copper sulfate-formamide solution of 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 smoke-suppressing and bird-repelling microcapsules. The electron micrograph is shown below. Figure 1 .

[0092] The smoke-suppressing and bird-repelling microcapsules obtained in step S8 and dodecyl dimethyl betaine were stirred and mixed at 300 rpm for 3 hours at room temperature to obtain a smoke-suppressing and bird-repelling asphalt additive. The mass ratio of the smoke-suppressing and bird-repelling microcapsules to dodecyl dimethyl betaine was 3:2.

[0093] Heat 100 parts of base asphalt to 143°C, add 20 parts of smoke-suppressing and bird-repelling asphalt additive at 400 rpm, and stir for 4 hours to obtain smoke-suppressing and bird-repelling asphalt.

[0094] Example 2

[0095] Except for step S2, which involves adding equal mass ratios of α-bromocinnamaldehyde, 2-chloro-3-phenylpropenal, methyl anthranilate, and butyl anthranilate to the second container, the rest of the steps are the same as in Example 1.

[0096] Example 3

[0097] The only difference is that when preparing smoke-suppressing and bird-repelling asphalt, the amount of smoke-suppressing and bird-repelling asphalt additive added is 15 parts by weight, and the rest is the same as in Example 1.

[0098] Example 4

[0099] The only difference is that when preparing the smoke-suppressing and bird-repelling asphalt additive, the dispersant is changed to 1-hydroxyethyl-carboxymethyl-alkylimidazoline, and the rest is the same as in Example 1.

[0100] Example 5

[0101] 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.

[0102] Example 6

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

[0104] Comparative Example 1

[0105] 100 parts of base asphalt were heated to 143°C, and 8 parts by mass of dodecyl dimethyl betaine were added at 400 rpm. The mixture was stirred for 4 hours to obtain an asphalt sample.

[0106] Comparative Example 2

[0107] S1: Add equal mass ratios of m-chlorocinnamaldehyde, 2-chloro-3-phenylpropenal, ethyl 2-aminobenzoate, and ethyl 2-dimethylaminobenzoate to the first container, and stir at 400 rpm for 5 minutes at 65°C to obtain the core material mixture.

[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. Stir at 400 rpm for 5 hours at 50°C.

[0109] 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 65°C to obtain Pickering emulsion.

[0110] 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 65°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 smoke-suppressing and bird-repelling microcapsule matrix.

[0111] S5: The smoke-suppressing and bird-repelling 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 mixture was stirred for 5 hours at 400 rpm and 60°C. The mass ratio of methanol, smoke-suppressing and bird-repelling 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.

[0112] 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.

[0113] 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 smoke-suppressing and bird-repelling microcapsules.

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

[0115] Heat 100 parts of base asphalt to 143°C, add 20 parts of smoke-suppressing and bird-repelling asphalt additive at 400 rpm, and stir for 4 hours to obtain smoke-suppressing and bird-repelling asphalt.

[0116] Comparative Example 3

[0117] 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 at 400 rpm for 5 hours at 160℃ to modify the surface of the nano-tourmaline powder. After modification, wash the modified nano-tourmaline powder with ethanol multiple times and vacuum dry at -30℃ for 5 hours for later use.

[0118] S2: Add equal mass ratios of m-chlorocinnamaldehyde, 2-chloro-3-phenylpropenal, ethyl 2-aminobenzoate, and ethyl 2-dimethylaminobenzoate to the second container, and stir at 400 rpm for 5 minutes at 65°C to obtain the core material mixture.

[0119] 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 65°C.

[0120] 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 65°C to obtain Pickering emulsion.

[0121] 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 65℃, 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℃ for 5 hours to obtain the smoke-suppressing and bird-repelling microcapsule matrix.

[0122] The smoke-suppressing and bird-repelling microcapsule matrix obtained from S5 and dodecyl dimethyl betaine were stirred and mixed at 300 rpm for 3 hours at room temperature to obtain a smoke-suppressing and bird-repelling asphalt additive. The mass ratio of the smoke-suppressing and bird-repelling microcapsule matrix to dodecyl dimethyl betaine was 3:2.

[0123] Heat 100 parts of base asphalt to 143°C, add 20 parts of smoke-suppressing and bird-repelling asphalt additive at 400 rpm, and stir for 4 hours to obtain smoke-suppressing and bird-repelling asphalt.

[0124] Test case

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

[0126] Table 1 Frequency of bird occurrences

[0127]

[0128]

[0129] The gases released by asphalt pavement under high temperature are mainly volatile organic compounds and sulfides. To verify the smoke suppression ability of the asphalt additive containing smoke suppressant and bird repellent described in this invention on asphalt materials, the samples prepared in the examples and comparative examples were spread on the surface of asphalt mixture 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.

[0130] Table 2 Asphalt Fume Test Data

[0131]

[0132]

[0133] It should be emphasized that the above-mentioned content is merely an embodiment of the present invention and should not be construed as limiting the specific implementation of the present invention to the above description. For researchers and those skilled in the art, 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. A smoke-suppressing and bird-repelling microcapsule, characterized in that: The shell material of the smoke-suppressing and bird-repelling microcapsule 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; 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 material, the mass ratio of silicon dioxide to nano-tourmaline is (1-5):1; The smoke-suppressing and bird-repelling microcapsules are prepared by the following method, including: 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 halogenated aromatic aldehydes and amino aromatic esters 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 smoke-suppressing and bird-repelling microcapsule matrix; S6: Disperse the smoke-suppressing and bird-repelling microcapsule matrix obtained in step S5 in a methanol dispersion, then add a methanol solution of coupling agent, 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: The solid powder obtained after drying in step S7 is ultrasonically dispersed in a metal ion salt-formamide solution and reacted under stirring. After the reaction is completed, the powder is filtered, washed, and freeze-dried to obtain smoke-suppressing and bird-repelling microcapsules.

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 with a diameter of 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 boiling point of the halogenated aromatic aldehyde is greater than 120°C; And / or, the boiling point of the amino aromatic ester is greater than 150°C.

5. The smoke-suppressing and bird-repelling microcapsule according to claim 4, characterized in that: The halogenated aromatic aldehyde is one or more of o-chlorocinnamaldehyde, m-chlorocinnamaldehyde, p-chlorocinnamaldehyde, 3-bromocinnamaldehyde, 3-chloro-2-(chloromethyl)cinnamaldehyde, 2-chloro-3-phenylpropenal, and α-bromocinnamaldehyde. And / or, the amino aromatic ester is one or more of methyl anthranilate, ethyl 2-aminobenzoate, ethyl 2-dimethylaminobenzoate, and butyl anthranilate.

6. The smoke-suppressing and bird-repelling microcapsule according to claim 1, characterized in that: 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 a smoke-suppressing and bird-repelling 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 halogenated aromatic aldehydes and amino aromatic esters 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 smoke-suppressing and bird-repelling microcapsule matrix; S6: Disperse the smoke-suppressing and bird-repelling microcapsule matrix obtained in step S5 in a methanol dispersion, then add a methanol solution of coupling agent, 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: The solid powder obtained after drying in step S7 is ultrasonically dispersed in a metal ion salt-formamide solution and reacted under stirring. After the reaction is completed, the powder is filtered, washed, and freeze-dried to obtain smoke-suppressing and bird-repelling microcapsules.

8. The preparation method according to claim 7, characterized in that: In step S1, the surfactant is a cationic surfactant; 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, and the mass ratio of the solvent to the surfactant is (20-40):

1.

9. The preparation 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 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℃; 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℃, 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℃, 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℃, 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.

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

12. The preparation method according to claim 11, characterized in that: In step S3, the solvent is at least one of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide.

13. 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.

14. The preparation 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.

15. The preparation method according to claim 7, characterized in that: In step S4, the shell material is at least one of methyl silicate, ethyl orthosilicate, tetraethyl orthosilicate, and butyl orthosilicate.

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

17. The preparation method according to claim 16, characterized in that: In step S6, the coupling agent is at least one of 3-chloropropyltrimethylsilane, (dichloromethyl)trimethylsilane, (trichloromethyl)trimethylsilane, and (chlorodifluoromethyl)trimethylsilane.

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

1.

19. The preparation method according to claim 7, characterized in that: The buffer solution mentioned in step S7 is either a phosphate buffer or a carbonate buffer; 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.

20. The preparation method according to claim 19, characterized in that: The buffer solution mentioned in step S7 is a carbonate buffer solution.

21. The preparation 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.

22. The preparation method according to claim 21, characterized in that: In step S7, the chelating agent is iminodiacetic acid, triethylenediamine, or hypotriacetic acid.

23. The preparation method according to claim 21, characterized in that: In step S7, the chelating agent is iminodiacetic acid.

24. The preparation 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.

25. A smoke-suppressing and bird-repelling asphalt additive, characterized in that: The ingredients, by weight, include the following: 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 any one of claims 7-24; Dispersant, 1-10 parts.

26. The smoke-suppressing and bird-repelling asphalt additive according to claim 25, characterized in that: The dispersant is one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

27. A smoke-suppressing and bird-repelling asphalt, characterized in that: The ingredients, by weight, include the following: Base bitumen, 100-300 parts; The smoke-suppressing and bird-repelling asphalt additive according to any one of claims 25-26, 1-50 parts.

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