Environmentally friendly, sunlight-resistant microcapsules, environmentally friendly, sunlight-resistant asphalt additives and their preparation methods

Abstract

The application discloses an environment-friendly sunlight-resistant microcapsule, an environment-friendly sunlight-resistant asphalt additive and a preparation method thereof. The environment-friendly sunlight-resistant microcapsule comprises a shell material and a core material, the shell material is a composite shell material comprising titanium dioxide / nano tourmaline / polydopamine, the core material is a normal alkane with a phase transition temperature of 40 DEG C-60 DEG C, and the surface of the shell material is loaded with a metal chelate and a light stabilizer. Through the temperature control effect, the ultraviolet aging resistance and the in-situ capture effect of the environment-friendly sunlight-resistant microcapsule, the disease of asphalt caused by high temperature and ultraviolet is reduced, the service time of the asphalt pavement is effectively prolonged, the amount of small molecule compounds released by the asphalt pavement under the influence of high temperature is reduced, and the environmental problems existing in the asphalt pavement are solved.

Description

Technical Field

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

[0002] Nowadays, with the rapid development of municipal transportation, asphalt roads are increasingly becoming the main form of road surface. Asphalt pavements have many advantages, such as low noise, high smoothness, and convenient construction. However, in sunny areas, prolonged exposure to sunlight can cause asphalt pavements to undergo ultraviolet aging, hardening and becoming brittle, making them prone to cracking. Furthermore, it can raise the pavement temperature, leading to softening of the asphalt and subsequent problems such as blistering, bleeding, and cracking, thus affecting the service life of the asphalt pavement. Additionally, it can cause small molecule compounds in the asphalt system to volatilize upon heating, further aging and brittlening the asphalt. These volatilized compounds can also react with vehicle exhaust under sunlight to generate photochemical smog, harming the ecological environment and affecting human health.

[0003] CN101434472A discloses a method for improving the UV aging resistance of modified asphalt. This method involves adding nanomaterials and UV absorbers with UV absorption capabilities to the asphalt to delay the effects of UV aging. However, these additives have poor compatibility with asphalt, affecting its road performance. Furthermore, these additives exhibit poor stability, resulting in significant losses during high-temperature mixing and subsequent heat absorption and warming of the road surface, severely impacting their UV resistance. Additionally, these additives fail to address the problems caused by high road surface temperatures resulting from sunlight exposure.

[0004] CN111303646A discloses a modified asphalt that achieves self-regulating temperature based on phase change microcapsules. This modified asphalt reduces pavement temperature by utilizing the heat-absorbing properties of the phase change in the microcapsule core material, thereby extending pavement service life. However, the shell material of these microcapsules has low strength, and the microcapsules are prone to breakage during asphalt mixing, weakening their pavement cooling performance. Furthermore, these microcapsules cannot solve a series of problems caused by UV aging of pavement.

[0005] In summary, existing technologies have not completely solved the series of problems caused by sunlight exposure on asphalt pavements of oil roads. Simply adding light stabilizers or phase change materials to asphalt does not result in asphalt materials with good resistance to ultraviolet aging, heat aging, or compatibility with asphalt. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides an environmentally friendly, sunlight-resistant microcapsule, an environmentally friendly, sunlight-resistant asphalt additive, and their preparation method. Through the temperature control, UV aging resistance, and in-situ trapping effects of the environmentally friendly, sunlight-resistant microcapsule, damage to asphalt caused by high temperatures and UV exposure is reduced, effectively extending the service life of asphalt pavements. Simultaneously, it reduces the amount of small molecule compounds released from asphalt pavements due to high temperatures, thus solving the environmental problems associated with asphalt pavements.

[0007] The first aspect of the present invention provides an environmentally friendly, sunlight-resistant microcapsule, the environmentally friendly, sunlight-resistant microcapsule comprising a shell material and a core material, the shell material being a composite shell material comprising titanium dioxide / nano tourmaline / polydopamine, the core material being a n-alkane with a phase transition temperature of 40℃-60℃, and the surface of the shell material being loaded with a metal chelate and a light stabilizer.

[0008] Furthermore, the light stabilizer is selected from one or more of benzophenone-based light stabilizers with more than 10 carbon atoms or hindered amine-based light stabilizers with more than 15 carbon atoms.

[0009] Furthermore, the benzophenone-based light stabilizer with more than 10 carbon atoms is selected from one or more of BP-1 (2,4-dihydroxybenzophenone), BP-2 (2,2',4,4'-tetrahydroxybenzophenone), BP-3 (4-methoxy-2-hydroxybenzophenone), BP-4 (2-hydroxy-4-methoxy-5-sulfonic acid benzophenone), BP-8 (2,2'-hydroxy-4-methoxybenzophenone), and BP-12 (2-hydroxy-4-n-octyloxybenzophenone).

[0010] Furthermore, the hindered amine light stabilizer with more than 15 carbon atoms is selected from HALS-770 (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate), HALS-292 (bis(1,2,2,6,6-pentamethylpiperidinol) sebacate), HALS-3346 (poly[(6-morpholino-1,3,5-triazine-2,4-yl)-((2,2,6,6-tetramethyl-4-piperidinyl)imine)hexane-((2,2,6,6-tetramethyl)... HALS-944 (poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexadiyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]), HALS-112 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate)).

[0011] Furthermore, the particle size of the environmentally friendly, sunlight-resistant microcapsules is 1-5 μm.

[0012] Furthermore, the mass ratio of the shell material to the core material of the environmentally friendly, sunlight-resistant microcapsule is 1:(0.5-2).

[0013] Furthermore, the shell material of the environmentally friendly, sunlight-resistant microcapsule is a composite shell material comprising titanium dioxide / nano tourmaline / polydopamine, wherein the mass ratio of titanium dioxide to nano tourmaline is (1-5):1, and the mass ratio of titanium dioxide to polydopamine shell material is 1:(0.1-0.5).

[0014] Furthermore, the shell material surface is loaded with a metal chelate, wherein the metal is preferably copper.

[0015] Furthermore, the shell material surface is loaded with metal chelates, the metal loading amount accounting for 0.1wt%-15wt% of the total mass of the environmentally friendly and sunlight-resistant microcapsules; the light stabilizer loading amount accounting for 0.1wt%-20wt% of the total mass of the environmentally friendly and sunlight-resistant microcapsules.

[0016] Furthermore, the n-alkane with a phase transition temperature of 40℃-60℃ is preferably one or more of n-octadecane, n-eicosane, and n-docosahexadecane.

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

[0018] S1: Nano tourmaline, surfactant and solvent are mixed and modified under stirring. After modification, the mixture is washed and freeze-dried to obtain modified nano tourmaline.

[0019] S2: Heat the core material raw material for later use;

[0020] S3: Add solvent and modified nano-tourmaline obtained in step S1 to the system of step S2, and stir to mix;

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

[0022] S5: Adjust the pH of the Pickering emulsion obtained in step S4 to 2-5, continue stirring, then age, filter, and freeze-dry;

[0023] S6: Add the solid powder obtained in step S5 to the buffer solution, add dopamine hydrochloride, stir and process, then filter, wash and freeze dry;

[0024] S7: Add the solid powder obtained in step S6 and the light stabilizer to an organic solvent, add a strong base, and react under reflux conditions. After cooling, filter, wash, and freeze-dry.

[0025] S8: Add the solid powder obtained in step S7 to the metal salt ion-formamide solution, stir and process. After the reaction is complete, filter, wash and freeze dry to obtain environmentally friendly sunlight-resistant microcapsules.

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

[0027] Further, the surfactant mentioned in step S1 is a cationic surfactant, preferably one or more of dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, and octadecyl trimethyl ammonium chloride.

[0028] Further, in step S1, the solvent is an aprotic solvent with a boiling point >100℃, preferably one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0029] Further, in step S1, the mass ratio of the nano-tourmaline to the surfactant is (1-10):1, and the mass ratio of the solvent to the surfactant is (5-60):1.

[0030] Further, in step S1, the stirring speed is 400-600 rpm; the modification temperature is 100-200℃; and the modification time is 4-10 hours.

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

[0032] Furthermore, in step S2, the heating temperature of the core material raw material is 40-60℃.

[0033] Further, in step S3, the solvent is an aprotic solvent with a boiling point >100℃, preferably one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoramide, and more preferably formamide.

[0034] Further, in step S3, the mass ratio of the core material raw material to the modified nano-tourmaline is (1-20):1. The mass ratio of the solvent to the modified nano-tourmaline is (10-80):1.

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

[0036] Further, in step S4, the titanium dioxide precursor is one or more of tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate.

[0037] Further, in step S4, the mass ratio of the core material raw material to the titanium dioxide precursor is 1:(0.5-2).

[0038] Furthermore, in step S4, the stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours.

[0039] Furthermore, in step S5, the pH can be adjusted using a dilute acid, such as dilute hydrochloric acid. The stirring speed is 400-600 rpm, the stirring temperature is 40-60℃, and the stirring time is 4-6 hours.

[0040] Further, in step S5, the aging conditions are: standing at 40-60°C for 12-30 hours. The freeze-drying conditions are: vacuum drying at -40--20°C for 4-8 hours.

[0041] Further, in step S6, the buffer solution is one or more of phosphate buffer, carbonate buffer, and tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer), preferably tris(hydroxymethyl)aminomethane hydrochloride buffer (Tris buffer).

[0042] Further, in step S6, the pH value of the buffer solution is 8-10.

[0043] Further, in step S6, the mass ratio of the buffer solution to the solid powder obtained in step S5 is (30-200):1.

[0044] Furthermore, in step S6, after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

[0045] Furthermore, in step S6, the stirring speed is 100-300 rpm, the stirring temperature is 20-30℃, and the stirring time is 12-24 hours.

[0046] Furthermore, in step S6, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0047] Furthermore, in step S7, the strong alkali is either solid KOH or solid NaOH, preferably solid KOH.

[0048] Furthermore, the organic solvent mentioned in step S7 is selected from one or more of methanol, butanediol, ethylene glycol, n-butanol, and anhydrous ethanol.

[0049] Furthermore, in step S7, the reaction temperature is 80-240℃, and the reaction time is 5-10 hours.

[0050] Further, in step S7, the mass ratio of the solid powder to the organic solvent is 1:(20-100), the mass ratio of the solid powder to the light stabilizer is 1:(20-80), and the mass ratio of the solid powder to the strong alkali is 1:(0.5-4).

[0051] Furthermore, in step S7, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0052] Furthermore, in step S8, the metal ion salt is preferably a copper ion salt, and more preferably anhydrous copper sulfate.

[0053] 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.

[0054] Furthermore, in step S8, the mass ratio of the metal ion salt-formamide solution to the solid powder obtained in step S7 is (10-100):1.

[0055] Furthermore, the stirring speed is 200-450 rpm, the stirring temperature is 100-190℃, and the stirring time is 2-5 hours.

[0056] Furthermore, in step S8, the freeze-drying conditions are: vacuum drying for 4-8 hours at a temperature of -40°C to -20°C.

[0057] A third aspect of this invention provides an environmentally friendly, sunlight-resistant asphalt additive, comprising the following components by weight:

[0058] The above-mentioned environmentally friendly, sunlight-resistant microcapsules, 1-5 parts;

[0059] Dispersant, 1-10 parts.

[0060] Furthermore, the dispersant is one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

[0061] Furthermore, environmentally friendly, sun-resistant microcapsules are added to a dispersant and mixed for 2-4 hours at a temperature of 25-45℃ and a stirring speed of 200-400 rpm to obtain an environmentally friendly, sun-resistant asphalt additive.

[0062] A fourth aspect of this invention provides an environmentally friendly, sunlight-resistant asphalt, comprising the following components by weight:

[0063] Base bitumen, 100-300 parts;

[0064] The above-mentioned environmentally friendly, sunlight-resistant asphalt additive, 1-30 parts.

[0065] Furthermore, the base asphalt is commercially available No. 50, No. 70 and No. 90 road asphalt, preferably No. 70 Grade A asphalt.

[0066] Furthermore, under a nitrogen atmosphere and at a temperature of 133-173℃, the base asphalt is heated to a molten state, and an environmentally friendly sunlight-resistant asphalt additive is added to the asphalt. After mixing at a stirring speed of 800-1000 rpm for 50-300 minutes, environmentally friendly sunlight-resistant asphalt is obtained.

[0067] Compared with the prior art, the present invention has the following advantages:

[0068] (1) The environmentally friendly and sun-resistant microcapsules of the present invention have three functions in their composite shell material. 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 precursor emulsion. The second function is that during the metal ion modification process of the microcapsule composite shell material, the negative ion field released by tourmaline can adsorb a large number of metal ions onto the surface of the microcapsule, effectively increasing the metal ion loading of the microcapsule shell material and further enhancing the smoke suppression ability of the environmentally friendly and sun-resistant microcapsules. The third function is that during the service of the road surface, after the environmentally friendly and sun-resistant microcapsules are heated, the nano-tourmaline contained inside the shell material will release a negative ion field, which will further attract the compounds released by the asphalt road surface under high temperature to the vicinity of the environmentally friendly and sun-resistant microcapsules. While increasing the difficulty of these compounds volatilizing, it can also make the metal ions on the surface of the microcapsules react with more of the above compounds, further inhibiting their volatilization, thereby effectively reducing the impact of the irritating gases released by the asphalt road surface on the human body.

[0069] (2) The present invention relates to environmentally friendly, sun-resistant microcapsules, wherein the titanium dioxide shell material can shield ultraviolet rays; the polydopamine shell material has a large number of active groups such as quinone groups and phenolic hydroxyl groups on its surface, which have good anti-ultraviolet ability. Utilizing the large number of active groups on the polydopamine shell surface, the light stabilizer is immobilized on the surface of the microcapsule through Schiff base reaction and Michael addition reaction. After immobilization, the stability of the light stabilizer is greatly improved, effectively avoiding the loss of light stabilizer due to heat, and possessing long-lasting and highly efficient anti-ultraviolet ability. After being added to asphalt, the composite shell material of the environmentally friendly, sun-resistant microcapsules can synergistically exert good anti-ultraviolet ability, effectively reducing the degree of ultraviolet aging during the service of asphalt pavement.

[0070] (3) The environmentally friendly and sun-resistant microcapsules of the present invention have metal ions on the surface of their composite shell material that can chemically react with small molecule compounds released by asphalt pavement under high temperature, effectively reducing the malodorous gases released by asphalt under high temperature and sun exposure, and avoiding discomfort to the human body caused by asphalt pavement.

[0071] (4) The environmentally friendly, sunlight-resistant microcapsule core material of the present invention can undergo a phase change to absorb heat when the asphalt temperature rises, effectively reducing the temperature of the asphalt pavement. It can not only reduce the amount of small molecule compounds released by the asphalt pavement, but also effectively reduce the damage caused by high temperature to the asphalt pavement and extend the service life of the asphalt pavement.

[0072] (5) The environmentally friendly, sunlight-resistant microcapsules of the present invention have an organic-inorganic multilayer composite shell material with high shell strength, which is not easy to break and has a long service life. Attached Figure Description

[0073] Figure 1 This is an electron microscope image of the environmentally friendly, sunlight-resistant microcapsules obtained in Example 1 of this invention. Detailed Implementation

[0074] To further illustrate the technical solution of the present invention, the present invention will be clearly and thoroughly described below in conjunction with embodiments.

[0075] The morphology test described in this invention is performed using a ZEISS Supra 55 scanning electron microscope with an accelerating voltage of 20kV. Since the microcapsule wall material is non-conductive, the sample needs to be sputtered with gold before testing.

[0076] The environmentally friendly, sunlight-resistant microcapsules of this invention were subjected to surface elemental analysis using a Bruker XFlash 6160 X-ray energy dispersive spectrometer to confirm that metal ions were successfully modified onto the surface of the microcapsules.

[0077] The flue gas generated during the use of the environmentally friendly, sunlight-resistant asphalt described in this invention was tested by gas chromatography, and the test items were non-methane total hydrocarbons and sulfides.

[0078] The base asphalt used in the following examples and comparative examples is Sinopec Donghai brand No. 70 Grade A asphalt.

[0079] Example 1

[0080] S1: Add tourmaline with a diameter of 70 nm, hexadecyltrimethylammonium bromide and formamide to the first container in a mass ratio of 2:1:40. Stir the reaction at 500 rpm and 190 °C for 6 hours to modify the surface of the nano-tourmaline. After the reaction is complete, wash the nano-tourmaline multiple times with ethanol and vacuum dry it at -30 °C for 5 hours to obtain the modified nano-tourmaline for later use.

[0081] S2: Add 5 parts by mass of n-dodecane to the second container and heat it at 50°C until it melts for later use;

[0082] S3: Add formamide at 50°C and the modified nano-tourmaline obtained in step S1 to the above system, and stir for 5 hours at 50°C and 500 rpm. The mass ratio of n-dodecane, modified nano-tourmaline and formamide is 5:2:50.

[0083] S4: Add 5 parts by mass of tetrabutyl titanate to the system of step S3, keep the stirring speed at 500 rpm and the temperature at 50°C unchanged, and continue stirring for 4 hours to obtain Pickering emulsion.

[0084] S5: Keeping the rotation speed of 500 rpm and the temperature of 50°C constant, slowly add 10 wt% dilute hydrochloric acid to the system of S4 using a peristaltic pump until the pH of the reaction system is 5. Continue stirring for 5 hours, then stop stirring and age for 24 hours while keeping the temperature constant. Then filter and wash the solid powder in the reaction system, and vacuum dry it at -30°C for 5 hours to obtain the environmentally friendly sunlight-resistant microcapsule precursor.

[0085] S6: Add 10 parts by weight of the environmentally friendly, sunlight-resistant microcapsule precursor to 100 parts by weight of Tris buffer solution with pH=8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 3 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0086] S7: Add the solid powder obtained in step S6 and the light stabilizers BP-1, BP-4 and HALS-770 in equal mass ratio to anhydrous ethanol, and further add solid KOH. The mass ratio of the solid powder obtained in step S6, the light stabilizer, the anhydrous ethanol and the solid KOH is 1:60:60:3. Reflux the reaction at 85°C for 10 hours. Then filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0087] S8: The solid powder obtained in step S7 was ultrasonically dispersed in a 50 wt% anhydrous copper sulfate-formamide solution. The mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution was 1:60. The mixture was stirred at 400 rpm and 140°C for 2 hours. After the reaction was completed, the bottom solid powder was filtered and washed, and then vacuum dried at -30°C for 5 hours to obtain environmentally friendly, sunlight-resistant microcapsules. The electron micrograph is shown below. Figure 1 .

[0088] An environmentally friendly, sunlight-resistant asphalt additive can be prepared by mixing 3 parts by weight of dodecyl dimethyl betaine with 2 parts by weight of environmentally friendly, sunlight-resistant microcapsules at 25°C and stirring at 200 rpm for 2 hours.

[0089] Under a nitrogen atmosphere and at a temperature of 155°C, 100 parts by weight of base asphalt are heated to a molten state. While maintaining the same gas and temperature conditions, 5 parts by weight of environmentally friendly sunlight-resistant asphalt additive are added to the asphalt. The mixture is stirred and mixed at 800 rpm for 100 minutes to obtain environmentally friendly sunlight-resistant asphalt.

[0090] Example 2

[0091] Except for step S7, where the light stabilizers are BP-2, BP-8, and HALS-944 in equal mass ratios, the rest is the same as in Example 1.

[0092] Example 3

[0093] Except for step S7, in which the mass ratio of the solid powder, light stabilizer, anhydrous ethanol, and KOH obtained in step S6 is 1:50:60:3, the rest is the same as in Example 1.

[0094] Example 4

[0095] Except that the dispersant used in the preparation of the environmentally friendly, sunlight-resistant asphalt additive is 1-hydroxyethyl-carboxymethyl-alkylimidazoline, the rest is the same as in Example 1.

[0096] Example 5

[0097] Except that when preparing the environmentally friendly, sunlight-resistant asphalt additive, the amount of dodecyl dimethyl betaine added is 4 parts by mass and the amount of environmentally friendly, sunlight-resistant microcapsules added is 1 part by mass, the rest is the same as in Example 1.

[0098] Example 6

[0099] Except that when preparing the environmentally friendly, sunlight-resistant asphalt additive, the amount of dodecyl dimethyl betaine added is 2 parts by mass, and the amount of environmentally friendly, sunlight-resistant microcapsules added is 3 parts by mass, the rest is the same as in Example 1.

[0100] Example 7

[0101] Except for step S3, where the mass ratio of n-dodecane, modified nano-tourmaline, and formamide is 5:1:50, the rest is the same as in Example 1.

[0102] Example 8

[0103] Except for step S8, where the mass ratio of solid powder to anhydrous copper sulfate-formamide solution is 1:50, the rest is the same as in Example 1.

[0104] Comparative Example 1

[0105] Steps S1-S5 are the same as in Example 1, and steps S6-S8 are omitted.

[0106] An environmentally friendly, sunlight-resistant asphalt additive can be obtained by mixing 3 parts by weight of dodecyl dimethyl betaine with 2 parts by weight of the environmentally friendly, sunlight-resistant microcapsule precursor prepared in step S5 at 25°C and stirring at 200 rpm for 2 hours.

[0107] Under a nitrogen atmosphere and at a temperature of 155°C, 100 parts by weight of base asphalt are heated to a molten state. While keeping the gas and temperature conditions constant, 5 parts by weight of environmentally friendly sunlight-resistant asphalt additive are added to the asphalt. The mixture is stirred and mixed at a speed of 800 rpm for 100 minutes to obtain environmentally friendly sunlight-resistant asphalt.

[0108] Comparative Example 2

[0109] Steps S1-S6 are the same as in Example 1;

[0110] S7: The solid powder obtained in step 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 1:60. The mixture is stirred and reacted at 400 rpm and 140°C for 2 hours. After the reaction is completed, the bottom solid powder is filtered and washed, and then vacuum dried at -30°C for 5 hours to obtain environmentally friendly sunlight-resistant microcapsules.

[0111] An environmentally friendly, sunlight-resistant asphalt additive can be prepared by mixing 3 parts by weight of dodecyl dimethyl betaine with 2 parts by weight of environmentally friendly, sunlight-resistant microcapsules at 25°C and stirring at 200 rpm for 2 hours.

[0112] Under a nitrogen atmosphere and at a temperature of 155°C, 100 parts by weight of base asphalt are heated to a molten state. While maintaining the same gas and temperature conditions, 5 parts by weight of environmentally friendly sunlight-resistant asphalt additive are added to the asphalt. The mixture is stirred and mixed at 800 rpm for 100 minutes to obtain environmentally friendly sunlight-resistant asphalt.

[0113] Comparative Example 3

[0114] Steps S1-S7 are the same as in Example 1, step S8 is omitted;

[0115] An environmentally friendly, sun-resistant asphalt additive can be prepared by mixing 3 parts by weight of dodecyl dimethyl betaine with 2 parts by weight of the solid powder obtained in step S7 at 25°C and stirring at 200 rpm for 2 hours.

[0116] Under a nitrogen atmosphere and at a temperature of 155°C, 100 parts by weight of base asphalt are heated to a molten state. While maintaining the same gas and temperature conditions, 5 parts by weight of environmentally friendly sunlight-resistant asphalt additive are added to the asphalt. The mixture is stirred and mixed at 800 rpm for 100 minutes to obtain environmentally friendly sunlight-resistant asphalt.

[0117] Comparative Example 4

[0118] The preparation of the environmentally friendly, sunlight-resistant microcapsules is the same as in Example 1.

[0119] Under a nitrogen atmosphere and at a temperature of 155°C, 100 parts by weight of base asphalt were heated to a molten state. While maintaining the same gas and temperature conditions, 2 parts by weight of environmentally friendly sunlight-resistant microcapsules were added to the asphalt. The mixture was stirred and mixed at 800 rpm for 100 minutes to obtain environmentally friendly sunlight-resistant asphalt.

[0120] Comparative Example 5

[0121] S1: Add 5 parts by mass of n-dodecane to the container and heat it at 50°C until it melts for later use;

[0122] S2: Add formamide and hexadecyltrimethylammonium bromide at 50°C to the above system, and stir for 5 hours at 50°C and 500 rpm. The mass ratio of n-dodecane, hexadecyltrimethylammonium bromide and formamide is 5:2:50.

[0123] S3: Add 5 parts by mass of tetrabutyl titanate to the system of step S2, keep the stirring speed of 500 rpm and the temperature of 50°C unchanged, and continue stirring for 4 hours to obtain Pickering emulsion.

[0124] S4: Keeping the rotation speed of 500 rpm and the temperature of 50°C constant, slowly add 10 wt% dilute hydrochloric acid to the system in step S3 using a peristaltic pump until the pH of the reaction system is 5. Continue stirring for 5 hours, then stop stirring and age for 24 hours while keeping the temperature constant. Then filter and wash the solid powder in the reaction system, and vacuum dry it at -30°C for 5 hours to obtain the environmentally friendly sunlight-resistant microcapsule precursor.

[0125] S5: Add 10 parts by weight of the environmentally friendly, sunlight-resistant microcapsule precursor to 100 parts by weight of Tris buffer solution with pH=8.5. The mass ratio of Tris buffer solution to solid powder is 80:1. Then add dopamine hydrochloride to make the concentration of dopamine in the reaction system 3 mg / mL. Stir at 200 rpm for 12 hours at 25°C and then stop stirring. Filter and wash the bottom solid powder and vacuum dry it at -30°C for 5 hours.

[0126] S6: Add the solid powder obtained in step S5 and the light stabilizers BP-1, BP-4 and HALS-770 in equal mass ratio to anhydrous ethanol, and further add solid KOH. The mass ratio of the solid powder obtained in step S5, the light stabilizer, the anhydrous ethanol and the solid KOH is 1:60:60:3. Reflux the reaction at 85°C for 10 hours. Then filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours.

[0127] S7: The solid powder obtained in step 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 1:60. The mixture is stirred and reacted at 400 rpm and 140°C for 2 hours. After the reaction is completed, the bottom solid powder is filtered and washed, and then vacuum dried at -30°C for 5 hours to obtain environmentally friendly sunlight-resistant microcapsules.

[0128] An environmentally friendly, sunlight-resistant asphalt additive can be prepared by mixing 3 parts by weight of dodecyl dimethyl betaine with 2 parts by weight of environmentally friendly, sunlight-resistant microcapsules at 25°C and stirring at 200 rpm for 2 hours.

[0129] Under a nitrogen atmosphere and at a temperature of 155°C, 100 parts by weight of base asphalt are heated to a molten state. While maintaining the same gas and temperature conditions, 5 parts by weight of environmentally friendly sunlight-resistant asphalt additive are added to the asphalt. The mixture is stirred and mixed at 800 rpm for 100 minutes to obtain environmentally friendly sunlight-resistant asphalt.

[0130] Comparative Example 6

[0131] Under a nitrogen atmosphere and at a temperature of 155°C, 100 parts by weight of base asphalt are heated to a molten state. While maintaining the same gas and temperature conditions, 3 parts by weight of dodecyl dimethyl betaine are added to the asphalt. The mixture is stirred and mixed at 800 rpm for 100 minutes to obtain environmentally friendly, sunlight-resistant asphalt.

[0132] Test Example 1

[0133] The UV aging test was conducted in a UV aging chamber with a UV intensity of 1200 μW / cm. 2 The aging temperature was 60℃, and the aging time was 10 days. After aging, the environmentally friendly, sunlight-resistant asphalt was subjected to routine asphalt performance analysis. The obtained data are shown in Table 1 below.

[0134] Table 1. Asphalt performance test and storage stability test data

[0135] Test sample Softening point / °C Needle penetration / 0.1mm Ductility 10℃ / cm Example 1 47.8 73 37.6 Example 2 47.9 73 37.7 Example 3 49.8 70 36.1 Example 4 47.9 74 37.7 Example 5 51.3 68 35.1 Example 6 50.2 69 35.8 Example 7 49.2 71 36.5 Example 8 48.7 72 36.9 Comparative Example 1 56.4 62 31.9 Comparative Example 2 54.0 65 33.3 Comparative Example 3 52.1 67 34.5 Comparative Example 4 55.0 63 32.7 Comparative Example 5 53.1 66 33.9 Comparative Example 6 57.4 61 30.6

[0136] Test Example 2

[0137] The environmentally friendly, sunlight-resistant asphalt samples prepared in the examples and comparative examples were made into rectangular samples of 10cm*10cm*3cm. The samples were then transferred into sealed containers with gas extraction ports and stored at 100°C for 1 day. After storage, the gas in the sealed container was extracted, and the content of non-methane total hydrocarbons and sulfides in the gas was tested by gas chromatography. The data obtained are shown in Table 2 below.

[0138] Table 2. Asphalt VOCs Test Data

[0139]

[0140]

[0141] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An environmentally friendly, sun-resistant microcapsule, characterized by: The environment-friendly sunlight-resistant microcapsule comprises a shell material and a core material, the shell material is a composite shell material comprising titanium dioxide / nano-electricite / polydopamine, the core material is n-alkane with a phase transition temperature of 40-60 DEG C, and the surface of the shell material is loaded with metal chelate and light stabilizer; The light stabilizer is selected from one or more of benzophenone light stabilizers with more than 10 carbon atoms or hindered amine light stabilizers with more than 15 carbon atoms; The surface of the shell material is loaded with metal chelate, wherein the metal is copper; The environment-friendly sunlight-resistant microcapsule is prepared by the following method, comprising: S1: mixing nano-electricite, surfactant and solvent, modifying under stirring, washing after modification, freeze-drying to obtain modified nano-electricite; S2: heating the core material raw material for standby; S3: adding solvent and modified nano-electricite obtained in step S1 to the system in step S2, stirring and mixing; S4: adding titanium dioxide precursor to the reaction system in step S3, stirring and mixing to obtain Pickering emulsion; S5: adjusting the pH value of the Pickering emulsion obtained in step S4 to 2-5, continuing to stir, then aging, filtering and freeze-drying; S6: adding the solid powder prepared in step S5 to buffer solution, adding dopamine hydrochloride, treating under stirring, then filtering, washing and freeze-drying; S7: adding the solid powder prepared in step S6 and light stabilizer to organic solvent, adding strong base and reacting under heating reflux condition, cooling, then filtering, washing and freeze-drying; S8: adding the solid powder prepared in step S7 to copper salt ion-formamide solution, treating under stirring, filtering, washing and freeze-drying after reaction to obtain the environment-friendly sunlight-resistant microcapsule.

2. The environmentally friendly sun light resistant microcapsule according to claim 1, characterized in that: The benzophenone light stabilizer with more than 10 carbon atoms is selected from one or more of 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2,2'-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone; The hindered amine light stabilizer with more than 15 carbon atoms is selected from one or more of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, sebacic acid bis(1,2,2,6,6-pentamethylpiperidinol) ester, poly[(6-morpholino-1,3,5-triazine-2,4-yl)-((2,2,6,6-tetramethyl-4-piperidyl) imino) hexane-((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly[[6-[(1,1,3,3-tetramethylbutyl) amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl) imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl) imino]] and bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate.

3. The environmentally friendly sunlight resistant microcapsule according to claim 1, characterized in that: The particle size of the environment-friendly sunlight-resistant microcapsule is 1-5 μm.

4. The environmentally friendly sunlight resistant microcapsule according to claim 1, characterized in that: The mass ratio of the shell material to the core material of the environment-friendly sunlight-resistant microcapsule is 1:(0.5-2). And / or, the mass ratio of titanium dioxide to nanometer tourmaline is (1-5):1, and the mass ratio of titanium dioxide to polydopamine shell material is 1:(0.1-0.5).

5. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: The metal loading amount of the shell material surface accounts for 0.1wt%-15wt% of the total mass of the environment-friendly sunlight-resistant microcapsule; and the light stabilizer loading amount accounts for 0.1wt%-20wt% of the total mass of the environment-friendly sunlight-resistant microcapsule.

6. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: The normal alkane with a phase transition temperature of 40-60 DEG C is one or more of n-octadecane, n-eicosane, and n-docosane.

7. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: The surface active agent in step S1 is a cationic surface active agent, and the solvent is an aprotic solvent with a boiling point >100 DEG C. And / or, the mass ratio of the nanometer tourmaline to the surface active agent is (1-10):1, and the mass ratio of the solvent to the surface active agent is (5-60):

1.

8. The environmentally friendly, sunlight resistant microcapsule according to claim 7, characterized in that: The surface active agent in step S1 is one or more of dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium bromide, and octadecyl trimethyl ammonium chloride, and the solvent is one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoryl amide.

9. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S1, the stirring speed is 400-600 rpm; the modification temperature is 100-200 DEG C, and the modification time is 4-10 hours. And / or, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60 DEG 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 DEG 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 DEG C, and the stirring time is 4-6 hours. And / or, in step S6, the stirring speed is 100-300 rpm, the stirring temperature is 20-30 DEG C, and the stirring time is 12-24 hours. And / or, in step S8, the stirring speed is 200-450 rpm, the stirring temperature is 100-190 DEG C, and the stirring time is 2-5 hours.

10. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S2, the core material raw material heating temperature is 40-60 DEG C.

11. The environmentally friendly, sunlight resistant microcapsule according to claim 1, wherein: In step S3, the solvent is an aprotic solvent with a boiling point >100 DEG C.

12. The environmentally friendly, sunlight resistant microcapsule of claim 11, wherein: In step S3, the solvent is one or more of formamide, N,N-dimethylformamide, dimethylacetamide, and dimethylphosphoryl amide.

13. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S3, the mass ratio of the core material raw material to the modified nanometer tourmaline is (1-20):1; and the mass ratio of the solvent to the modified nanometer tourmaline is (10-80):

1.

14. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S4, the titanium dioxide precursor is one or more of n-butyl titanate, tetra-n-propyl titanate, and tetraethyl titanate. And / or, the mass ratio of the core material raw material to the titanium dioxide precursor is 1:(0.5-2).

15. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S6, the buffer is one or more of phosphate buffer, carbonate buffer, and tris-hydroxymethyl aminomethane hydrochloride buffer. And / or, the pH value of the buffer is 8-10. And / or, the mass ratio of the buffer to the solid powder prepared in step S5 is (30-200):

1.

16. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S6, after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

17. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S7, the strong base is one of solid KOH and solid NaOH. And / or, the organic solvent is one or more of methanol, butanediol, ethylene glycol, n-butanol, and anhydrous ethanol. And / or, the mass ratio of the solid powder to the organic solvent is 1:(20-100), the mass ratio of the solid powder to the light stabilizer is 1:(20-80), and the mass ratio of the solid powder to the strong base is 1:(0.5-4).

18. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S7, the temperature of the reaction is 80-240°C, and the reaction time is 5-10 hours.

19. The environmentally friendly, sunlight resistant microcapsule of claim 1, wherein: In step S8, in the copper ion salt-formamide solution, the mass ratio of the copper ion salt to formamide is (0.5-1.5):

1. And / or, the mass ratio of the copper ion salt-formamide solution to the solid powder prepared in step S7 is (10-100):

1.

20. An environmentally friendly, sunlight resistant asphalt additive, characterized by: By weight parts Comprise the following components: The environmentally friendly sunlight-resistant microcapsule according to any one of claims 1-19, 1-5 parts; A dispersant, 1-10 parts.

21. The environmentally friendly, sunlight resistant asphalt additive according to claim 20, characterized in that: The dispersant is one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

22. An environmentally friendly, sunlight resistant asphalt, characterized in that: By weight parts, the following components are included: Matrix asphalt, 100-300 parts; The environmentally friendly sunlight-resistant asphalt additive according to any one of claims 20-21, 1-30 parts.

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