Odor-free temperature-control asphalt additive, odor-free temperature-control asphalt and preparation method of odor-free temperature-control asphalt

Abstract

The invention discloses an odorless temperature-controlled asphalt additive, odorless temperature-controlled asphalt and a preparation method of the odorless temperature-controlled asphalt. The odorless temperature control asphalt additive comprises the following components in parts by weight: 1-5 parts of odorless temperature control microcapsules; 1-5 parts of an auxiliary deodorant; 1-5 parts of a dispersant; the odor-removing temperature-control microcapsule comprises a composite shell material and a core material, the composite shell material comprises silicon dioxide / nano tourmaline / polydopamine, the core material comprises n-alkane with the phase change temperature of 40-60 DEG C, and a metal chelate and a smoke suppression compound containing active alpha-H are loaded on the surface of the composite shell material. The odorless temperature-controlled asphalt additive can efficiently and durably reduce the content of irritant gas in asphalt smoke, reduce the content of volatile organic compounds released by an asphalt pavement at high temperature, improve the high-temperature stability of asphalt and prolong the service time of the asphalt pavement, and provides a brand new idea for long-life and environment-friendly utilization of asphalt.

Description

Technical Field

[0001] The invention belongs to the field of special asphalt, and specifically relates to a odor-free temperature-controlling asphalt additive, odor-free temperature-controlling asphalt and a preparation method thereof. Background Art

[0002] At present, asphalt roads are the main type of traffic roads due to their advantages such as good road performance, high flatness, low road noise and easy production. However, there are many problems in the production, construction, storage, transportation and pavement application of asphalt, such as: the hot mix and hot paving process used in asphalt construction is prone to produce toxic, harmful and irritating fumes, which affect the ecological environment and threaten human health; asphalt has a strong heat absorption capacity, and the temperature of the asphalt pavement will quickly rise to a higher temperature under the scorching sun, which will not only cause the asphalt to soften, but also cause a series of diseases such as rutting, lumps, and oiling, reducing the service life of asphalt, but also cause the asphalt to release volatile organic compounds, thereby generating haze and photochemical smog, affecting the ecological environment and human health. In addition, high-temperature asphalt pavements will continuously release a large amount of heat into the environment, exacerbating the urban heat island effect.

[0003] At present, the prior art generally solves the above problems by adding admixtures to asphalt, among which the two most commonly used admixtures are phase change materials and deodorizers. Adding phase change materials to the asphalt system can improve a series of problems caused by the asphalt absorbing heat and heating. However, the asphalt material obtained by this method is usually greatly affected by the basic properties of asphalt due to the poor compatibility between the phase change material and asphalt, and the asphalt material obtained by this method can only reduce the amount of volatile organic matter released by the asphalt pavement under high temperature conditions to a certain extent, and cannot reduce the amount of smoke generated during the asphalt construction process; adding deodorizers to asphalt can make the deodorizers react with the volatile light components in the asphalt to generate macromolecular compounds, which can reduce the amount of smoke generated during the asphalt construction process to a certain extent. However, this method can only reduce the amount of smoke generated during the asphalt construction process, and cannot reduce the amount of volatile organic matter released by the asphalt pavement under high temperature. And the macromolecular compounds generated after the deodorizers used react with the light components in the asphalt are still relatively unstable: on the one hand, during the hot storage of asphalt, the molecular chains of these macromolecular compounds may break, causing the light components to detach, and then volatilize under heat to produce asphalt smoke. On the other hand, these macromolecular compounds may directly volatilize and produce asphalt fumes after coming into contact with high-temperature stones during the asphalt mixing and construction process. Summary of the invention

[0004] In view of the problems existing in the prior art, the present invention provides a deodorizing temperature-controlling asphalt additive, a deodorizing temperature-controlling asphalt and a preparation method thereof. The deodorizing temperature-controlling asphalt prepared by adding deodorizing temperature-controlling microcapsules to asphalt, with the help of the temperature-controlling effect of the microcapsules and the deodorizing effect of the deodorizing active components on their surface, achieves the triple purpose of effectively and persistently reducing the content of irritating gases in asphalt smoke, reducing the content of volatile organic matter released at high temperatures on asphalt pavements, and improving the high-temperature stability of asphalt, thereby extending the service life of asphalt pavements, providing a new idea for the long life and environmentally friendly use of asphalt.

[0005] The first aspect of the present invention provides a odorless temperature-controlling asphalt additive, comprising the following components in parts by weight:

[0006] Odor-free temperature-control microcapsules, 1-5 portions;

[0007] Auxiliary deodorant, 1-5 parts;

[0008] Dispersant, 1-5 parts;

[0009] The odor-free temperature-controlling microcapsule comprises a composite shell material and a core material, wherein the composite shell material comprises silicon dioxide / nano-tourmaline / polydopamine, the core material comprises normal alkanes with a phase transition temperature of 40-60°C, and the surface of the composite shell material is loaded with metal chelates and smoke-suppressing compounds containing active α-H.

[0010] Furthermore, the auxiliary deodorant is selected from one or more phosphite antioxidants having a boiling point greater than 220°C.

[0011] Furthermore, the phosphite antioxidant with a boiling point greater than 220° C. is selected from one or more of tris(2,4-di-tert-butylbenzene) phosphite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphospiro[5.5]undecane, tris(nonylphenol) phosphite, antioxidant 1500 (4,4'-isopropyl diphenyl C12-15-ol phosphite), and distearyl pentaerythritol diphosphite.

[0012] Furthermore, the dispersant is selected from one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

[0013] Furthermore, the particle size of the odor-free temperature-controlling microcapsules is 1-5 μm.

[0014] Furthermore, the mass ratio of the composite shell material to the core material of the odor-free temperature-controlling microcapsule is 1:(0.5-2).

[0015] Furthermore, the composite shell material of the odor-free temperature-controlling microcapsule includes silicon dioxide / nano-tourmaline / polydopamine, wherein the mass ratio of silicon dioxide to nano-tourmaline is (1-5):1, and the mass ratio of silicon dioxide to polydopamine is 1:(0.1-0.5).

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

[0017] Furthermore, the surface of the composite shell material is loaded with a metal chelate, wherein the metal is preferably copper.

[0018] Furthermore, the shell material surface is loaded with metal chelates and smoke suppressant compounds containing active α-H, the metal loading accounts for 0.1wt%-15wt% of the total mass of the odor-free temperature-controlling microcapsules; the smoke suppressant compound loading containing active α-H accounts for 0.1wt%-20wt% of the total mass of the odor-free temperature-controlling microcapsules.

[0019] Furthermore, the smoke suppressant compound containing active α-H is selected from one or more of aldehyde compounds having a carbon number greater than 9 or ketone compounds having a carbon number greater than 8.

[0020] Furthermore, the aldehyde compound having a carbon number greater than 9 is selected from one or more of o-methylcinnamaldehyde, p-methylcinnamaldehyde, anisaldehyde, 2-methylundecanal, 10-undecanal, ethyl vanillin, benzaldehyde, phenylacetaldehyde, p-hydroxybenzaldehyde, butylphenylmethylpropionaldehyde, neral, hydroxymethylpentylcyclohexene acetal, 3-(4-ethylphenyl)-2,2-dimethylpropionaldehyde, vanillin propylene glycol acetal, methylhexylcinnamaldehyde, methylpentylcinnamaldehyde, and diethylaminobenzaldehyde.

[0021] Furthermore, the ketone compound having a carbon number greater than 8 is selected from one or more of carvone, 3-hydroxy-2-butanone, 2,3-butanedione 3-pentene-2-one, and 6-methyl-3,5-heptadien-2-one.

[0022] Furthermore, the preparation method of the odor-free temperature-controlling microcapsule comprises the following steps:

[0023] S1: mixing nano-tourmaline, a surfactant and a solvent, modifying the mixture under stirring, washing the mixture after the modification, and freeze-drying the mixture to obtain modified nano-tourmaline;

[0024] S2: heating the core material raw material until it is melted, then adding the solvent and the modified nano-tourmaline obtained in step S1, and stirring and mixing;

[0025] S3: adding a silicon dioxide precursor to the reaction system in step S2, stirring and mixing, and obtaining a Pickering emulsion;

[0026] S4: adjusting the pH value of the Pickering emulsion obtained in step S3 to 2-5, stirring and then aging, filtering, washing, and freeze-drying;

[0027] S5: adding the solid powder obtained in step S4 to a buffer solution, adding dopamine hydrochloride, treating under stirring, and then filtering, washing, and freeze-drying;

[0028] S6: adding the solid powder obtained in step S5, the smoke suppressant compound containing active α-H, and a strong base to an organic solvent, reacting under heating reflux conditions, cooling, filtering, washing, and freeze-drying;

[0029] S7: ultrasonically dispersing the solid powder obtained in step S6 in a metal ion salt-formamide solution, reacting under stirring, and after the reaction is completed, filtering, washing, and freeze-drying to obtain odor-free temperature-controlling microcapsules.

[0030] Furthermore, in step S1, the diameter of the nano-tourmaline is 10-100 nm.

[0031] Furthermore, in step S1, the surfactant is a cationic surfactant, preferably at least one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride, and octadecyltrimethylammonium chloride, and more preferably cetyltrimethylammonium bromide.

[0032] 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.

[0033] Furthermore, 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 (5-50):1.

[0034] Furthermore, in step S1, the stirring speed is 200-500 rpm; the modification temperature is 100-190° C., and the modification time is 2-5 hours.

[0035] Furthermore, in step S1, the freeze-drying conditions are: vacuum drying at a temperature of -40°C to -20°C for 4-8 hours.

[0036] Furthermore, in step S2, the core material raw material is heated to a melting temperature of 40-60°C.

[0037] Furthermore, in step S2, 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.

[0038] Furthermore, in step S2, the mass ratio of the core material raw material to the modified nano-tourmaline is (1-10):1, and the mass ratio of the solvent to the modified nano-tourmaline is (20-80):1.

[0039] Furthermore, in step S2, the stirring speed is 400-600 rpm, the stirring temperature is 40-60° C., and the stirring time is 4-6 hours.

[0040] Furthermore, in step S3, the silicon dioxide precursor is a silicate compound, preferably at least one of methyl silicate, ethyl orthosilicate, tetraethyl orthosilicate, and butyl orthosilicate, and more preferably ethyl orthosilicate.

[0041] Furthermore, in step S3, the mass ratio of the core material raw material to the silica precursor is (0.5-1.5):1.

[0042] Furthermore, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60° C., and the stirring time is 4-6 hours.

[0043] Furthermore, in step S4, the pH may be adjusted by dropwise addition of dilute acid, such as dropwise addition of dilute hydrochloric acid.

[0044] Furthermore, in step S4, the stirring speed is 400-600 rpm, the stirring temperature is 40-60° C., and the stirring time is 4-6 hours.

[0045] Furthermore, in step S4, the aging condition is: standing at 40-60°C for 12-30 hours. The freeze-drying condition is: vacuum drying at a temperature of -40--20°C for 4-8 hours.

[0046] Furthermore, in step S5, the buffer is one or more of phosphate buffer, carbonate buffer, and Tris buffer, preferably Tris buffer.

[0047] Furthermore, in step S5, the pH value of the buffer solution is preferably 8-10.

[0048] Furthermore, in step S5, the mass ratio of the buffer solution to the solid powder obtained in step S4 is (10-100):1.

[0049] Furthermore, in step S5, after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

[0050] Furthermore, in step S5, the stirring speed is 100-300 rpm, the stirring temperature is 20-40° C., and the stirring time is 12-24 hours.

[0051] Furthermore, in step S5, the freeze-drying conditions are: vacuum drying at a temperature of -40°C to -20°C for 4-8 hours.

[0052] Furthermore, in step S6, the organic solvent is selected from one or more of methanol, butanediol, ethylene glycol, n-butanol, and anhydrous ethanol, preferably anhydrous ethanol.

[0053] Furthermore, in step S6, the mass ratio of the solid powder obtained in step S5 to the smoke suppressant compound containing active α-H is 1:(10-40). The mass ratio of the solid powder obtained in step S5 to the organic solvent is 1:(20-80). The mass ratio of the solid powder obtained in step S5 to the strong base is 1:(0.5-2).

[0054] Furthermore, in step S6, the strong base is one of solid KOH and solid NaOH, preferably solid KOH.

[0055] Furthermore, in step S6, the reaction conditions of heating and reflux are: reaction temperature is 80-220° C., and reaction time is 5-10 hours.

[0056] Furthermore, in step S6, the freeze-drying conditions are: vacuum drying at a temperature of -40°C to -20°C for 4-8 hours.

[0057] Further, in step S7, the metal ion salt is preferably a copper ion salt, and more preferably anhydrous copper sulfate.

[0058] Furthermore, in step S7, in the metal ion salt-formamide solution, the mass ratio of the metal ion salt to formamide is (0.5-1.5):1.

[0059] Furthermore, in step S7, the mass ratio of the metal ion salt-formamide solution to the solid powder obtained in step S6 is (5-30):1.

[0060] Furthermore, in step S7, the stirring speed is 200-450 rpm, the reaction temperature is 100-190° C., and the reaction time is 2-5 hours.

[0061] Furthermore, in step S7, the freeze-drying conditions are: vacuum drying at a temperature of -40°C to -20°C for 4-8 hours.

[0062] Furthermore, the auxiliary deodorant is added to the dispersant, and the mixture is stirred at 400-500 rpm for 1-3 hours at 25-45°C, and then the deodorizing temperature-controlling microcapsules are added, and stirring is continued for 1-2 hours to obtain the deodorizing temperature-controlling asphalt additive.

[0063] The second aspect of the present invention provides a deodorizing temperature-controlling asphalt, which comprises the following components by weight:

[0064] Base asphalt, 50-500 parts;

[0065] The above-mentioned odorless temperature-controlling asphalt additive, 1-50 parts.

[0066] Furthermore, the base asphalt is commercially available No. 50, No. 70 and No. 90 road asphalt, preferably No. 70 Grade A asphalt.

[0067] Furthermore, the base asphalt is heated to 133-153° C., and the odor-free temperature-controlling asphalt additive is added at a rotation speed of 400-600 rpm, and stirred for 2-4 hours to obtain the odor-free temperature-controlling asphalt.

[0068] Compared with the prior art, the present invention has the following advantages:

[0069] (1) The odor-free and temperature-controlling microcapsules in the odor-free and temperature-controlling asphalt additive of the present invention have a composite shell material with three functions. The first function is that during the preparation process, nano-tourmaline serves as a template for the synthesis of microcapsules, which can maintain the stability of normal alkane 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 microcapsule surface by means of the negative ion field released by the nano-tourmaline under high temperature conditions, effectively increasing the metal ion loading capacity of the microcapsule shell material, and further improving the smoke suppression ability of the odor-free and temperature-controlling microcapsules. The third function is that during the hot storage, mixing, and road use of asphalt, the nano-tourmaline contained in the shell material of the odor-free and temperature-controlling microcapsules will release a negative ion field under the action of high temperature, further attracting the compounds released by the asphalt under the action of high temperature to the vicinity of the odor-free and temperature-controlling microcapsules, while increasing the difficulty of these compounds to volatilize, and at the same time, the metal ions and smoke suppression compounds on the surface of the microcapsules can react with more of the above compounds, thereby effectively reducing the impact of the irritating gases released during asphalt mixing and asphalt pavement service on the human body.

[0070] (2) The odor-free temperature-controlling microcapsules of the present invention have a large number of active sites on the surface of the polydopamine shell, which can undergo Michael addition reaction with the smoke-suppressing compound containing active α-H of the present invention, so that the smoke-suppressing compound containing active α-H is very firmly fixed on the surface of the microcapsules to prevent it from physical migration and volatilization, further improving the binding ability of the microcapsules and asphalt, while improving the storage stability of the odor-free temperature-controlling asphalt without affecting other properties of the asphalt. In addition, after reacting with the smoke-suppressing compound containing active α-H, a large number of catechol groups are generated on the surface of the polydopamine, providing a large number of active sites for the subsequent chelation of metal ions.

[0071] (3) Compared with the chemical deodorizers used in traditional deodorizing asphalt, the deodorizing temperature-controlling microcapsules of the present invention have the disadvantages of poor storage stability and poor high-temperature stability. The smoke-suppressing compounds containing α-H modified by chemical reactions on the surface are connected to the wall material of the microcapsules and therefore have extremely strong stability. They will not volatilize or degrade due to high temperatures, thereby reducing the deodorizing effect.

[0072] (4) The odor-free and temperature-controlling microcapsules described in the present invention have a large number of metal ions modified on their surface through chelation. These metal ions have empty orbitals. After the microcapsules enter the asphalt system, the metal ions can directly accept the unshared electrons of some relatively active sulfur-containing and nitrogen-containing pollutants with pungent odors in the asphalt and form coordination bonds, thereby stably fixing the above-mentioned compounds on the surface of the microcapsules, effectively preventing them from volatilizing into the air under high temperature conditions, and further reducing the harm of asphalt smoke to the environment and human body.

[0073] (5) The odorless temperature-controlling asphalt additive of the present invention can control the temperature of the road surface in situ, which can not only effectively improve the high-temperature performance of asphalt, but also reduce the damage to the road surface caused by temperature changes, thereby extending the service life of the asphalt road surface.

[0074] (6) The odorless temperature-controlling asphalt additive of the present invention, after being added to asphalt materials, can reduce the road surface temperature without affecting the low-temperature performance of the road surface. It can not only effectively reduce the urban heat island effect, but also prevent the asphalt road surface from releasing volatile organic compounds due to excessive temperature, thereby avoiding the generation of photochemical smog and haze. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 The odor-free temperature-controlling microcapsule obtained in Example 1 of the present invention;

[0076] Figure 2 These are the temperature control performance test data of the odorless temperature-controlling asphalt and the base asphalt obtained in Example 1 and Comparative Example 6 of the present invention. DETAILED DESCRIPTION

[0077] To further illustrate the technical solution of the present invention, the present invention will be clearly and detailed described below in conjunction with embodiments.

[0078] The odor-free temperature-controlling microcapsules of the present invention are tested for morphology by scanning electron microscopy, and the acceleration voltage used is 20 kV. Since the wall material of the microcapsule is not conductive, the sample needs to be treated with gold spraying before the test.

[0079] The odor-free temperature-controlling microcapsules of the present invention are subjected to surface element testing by an X-ray spectrometer to confirm that the metal ions are successfully modified on the surface of the microcapsules; the sulfides in the odor-free asphalt flue gas of the present invention are tested by an Agilent 7890 gas chromatograph according to the national standard GBT14678-1993 Air quality hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl disulfide gas chromatography method.

[0080] The base asphalt used in the following examples and comparative examples is Sinopec Donghai brand No. 70 Grade A asphalt.

[0081] Example 1

[0082] S1: Add nano-tourmaline with a particle size of 90 nm, hexadecyltrimethylammonium bromide and formamide in a mass ratio of 5:1:50 into a first container, stir at 180°C and 400 rpm for 5 hours, then wash with ethanol for multiple times, and vacuum dry at -30°C for 5 hours to obtain modified nano-tourmaline for standby use;

[0083] S2: Add n-docosane to the second container, heat to melt at 50° C., then add formamide and the modified nano-tourmaline obtained in step S1, the mass ratio of n-docosane, the modified nano-tourmaline obtained in step S1 and formamide is 4:1:50, and stir at 50° C. and 400 rpm for 5 hours;

[0084] S3: adding tetraethyl orthosilicate to the reaction system of step S2, wherein the mass ratio of n-docosane to tetraethyl orthosilicate is 1:1, and continuing to stir at a speed of 400 rpm at 50° C. for 5 hours to obtain a Pickering emulsion;

[0085] S4: Use a peristaltic pump to slowly add 10 wt % dilute hydrochloric acid to the reaction system of step S3 until the pH of the reaction system is 4, continue stirring at 400 rpm at 50° C. for 5 hours, then stop stirring, keep the temperature unchanged and age for 24 hours, then filter and wash the solid powder in the reaction system, and vacuum dry it at -30° C. for 5 hours;

[0086] S5: adding the solid powder obtained in step S4 to a Tris buffer solution with a pH value of 8.5, wherein the mass ratio of the Tris buffer solution to the solid powder is 50:1, then adding dopamine hydrochloride to make the concentration of dopamine in the reaction system 4 mg / mL, stirring at 200 rpm at 25° C. for 12 hours, then stopping stirring, filtering and washing the bottom solid powder, and vacuum drying at a temperature of -30° C. for 5 hours;

[0087] S6: Manually stir the smoke suppressant compounds of equal mass ratio: 2-methylundecanal, 10-undecanal, carvone, 3-hydroxy-2-butanone, and then add the solid powder, anhydrous ethanol, and solid KOH obtained in step S5, wherein the mass ratio of the solid powder, the smoke suppressant compound, anhydrous ethanol, and KOH obtained in step S5 is 1:20:40:1, and then react under heating reflux at 90°C for 6 hours, and then filter and wash the bottom solid powder, and vacuum dry it at -30°C for 5 hours;

[0088] S7: Ultrasonic dispersion of the solid powder obtained in step S6 in a 50wt% anhydrous copper sulfate-formamide solution, the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution being 1:30, stirring and reacting at 400 rpm and 140°C for 2 hours, filtering and washing the bottom solid powder after the reaction, and vacuum drying at -30°C for 5 hours to obtain a tasteless temperature-controlled microcapsule, the electron microscope image of which is shown in FIG. Figure 1 .

[0089] The auxiliary deodorant antioxidant 1500 was added to dodecyl dimethyl betaine, and the mixture was stirred at 300 rpm for 3 hours at a temperature of 45°C, and then the deodorant temperature-controlling microcapsules prepared above were added, and the mixture was stirred for 1 hour to obtain the deodorant temperature-controlling asphalt additive. The mass ratio of the auxiliary deodorant, the deodorant temperature-controlling microcapsules, and the dodecyl dimethyl betaine was 1:1:1.

[0090] Heat 50 parts by mass of base asphalt to 143°C, add 6 parts by mass of odor-free temperature-controlling asphalt additive at a rotation speed of 500 rpm, and stir for 4 hours to obtain odor-free temperature-controlling asphalt.

[0091] Example 2

[0092] Except that the smoke suppression compounds in step S6 are neral, anisaldehyde, 2,3-butanedione 3-penten-2-one, and 6-methyl-3,5-heptadien-2-one in equal mass ratios, the rest is the same as in Example 1.

[0093] Example 3

[0094] Except that when preparing the odor-free temperature-controlling asphalt additive, the auxiliary odor-free agent is tris(nonylphenol) phosphite, and the rest is the same as Example 1.

[0095] Example 4

[0096] Except that in step S2, the mass ratio of n-docosane, the modified nano-tourmaline obtained in step S1 and formamide is 6:1:50, the rest is the same as that in embodiment 1.

[0097] Example 5

[0098] Except that in step S7, the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution is 1:20, the rest is the same as that of Example 1.

[0099] Example 6

[0100] Except for step S6, the mass ratio of the solid powder, smoke suppressant compound, anhydrous ethanol and KOH obtained in step S5 is 1:10:40:1, and the rest is the same as that of embodiment 1.

[0101] Example 7

[0102] When removing the odor-removing and temperature-controlling asphalt additive, the mass ratio of the auxiliary odor-removing agent, the odor-removing and temperature-controlling microcapsule, and dodecyl dimethyl betaine is 2.5:1:2.5, and the rest is the same as in Example 1.

[0103] Comparative Example 1

[0104] Steps S1-S6 are the same as those in Example 1, except that step S7 is omitted, and the solid powder obtained in step S6 is directly used to prepare a odorless temperature-controlling asphalt additive, as follows:

[0105] The auxiliary deodorant antioxidant 1500 is added to dodecyl dimethyl betaine, and the mixture is stirred at 300 rpm for 3 hours at a temperature of 45°C, and then the solid powder obtained in step S6 is added, and the mixture is stirred for 1 hour to obtain a deodorant temperature-controlling asphalt additive. The mass ratio of the auxiliary deodorant, the solid powder obtained in step S6, and dodecyl dimethyl betaine is 1:1:1.

[0106] Heat 50 parts by mass of base asphalt to 143°C, add 6 parts by mass of odor-free temperature-controlling asphalt additive at a rotation speed of 500 rpm, and stir for 4 hours to obtain odor-free temperature-controlling asphalt.

[0107] Comparative Example 2

[0108] S1: Add nano-tourmaline with a particle size of 90 nm, hexadecyltrimethylammonium bromide and formamide in a mass ratio of 5:1:50 into a first container, stir at 180°C and 400 rpm for 5 hours, then wash with ethanol for multiple times, and vacuum dry at -30°C for 5 hours to obtain modified nano-tourmaline for standby use;

[0109] S2: Add n-docosane to the second container, heat to melt at 50° C., then add formamide and the modified nano-tourmaline obtained in step S1, the mass ratio of n-docosane, the modified nano-tourmaline obtained in step S1 and formamide is 4:1:50, and stir at 50° C. and 400 rpm for 5 hours;

[0110] S3: adding tetraethyl orthosilicate to the reaction system of step S2, wherein the mass ratio of n-docosane to tetraethyl orthosilicate is 1:1, and continuing to stir at a speed of 400 rpm at 50° C. for 5 hours to obtain a Pickering emulsion;

[0111] S4: Use a peristaltic pump to slowly add 10 wt % dilute hydrochloric acid to the reaction system of step S3 until the pH of the reaction system is 4, continue stirring at 400 rpm at 50° C. for 5 hours, then stop stirring, keep the temperature unchanged and age for 24 hours, then filter and wash the solid powder in the reaction system, and vacuum dry it at -30° C. for 5 hours;

[0112] S5: adding the solid powder obtained in step S4 to a Tris buffer solution with a pH value of 8.5, wherein the mass ratio of the Tris buffer solution to the solid powder is 50:1, then adding dopamine hydrochloride to make the concentration of dopamine in the reaction system 4 mg / mL, stirring at 200 rpm at 25° C. for 12 hours, then stopping stirring, filtering and washing the bottom solid powder, and vacuum drying at a temperature of -30° C. for 5 hours;

[0113] S6: Ultrasonic dispersion of the solid powder obtained in step S5 in a 50wt% anhydrous copper sulfate-formamide solution, wherein the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution is 1:30, and the mixture is stirred at 400 rpm and 140°C for 2 hours. After the reaction is completed, the bottom solid powder is filtered and washed, and vacuum dried at -30°C for 5 hours to obtain odor-free temperature-controlling microcapsules.

[0114] The auxiliary deodorant antioxidant 1500 was added to dodecyl dimethyl betaine, and the mixture was stirred at 300 rpm for 3 hours at a temperature of 45°C, and then the deodorant temperature control microcapsules were added, and the mixture was stirred for 1 hour to obtain the deodorant temperature control asphalt additive. The mass ratio of the auxiliary deodorant, the deodorant temperature control microcapsules, and the dodecyl dimethyl betaine was 1:1:1.

[0115] Heat 50 parts by mass of base asphalt to 143°C, add 6 parts by mass of odor-free temperature-controlling asphalt additive at a rotation speed of 500 rpm, and stir for 4 hours to obtain odor-free temperature-controlling asphalt.

[0116] Comparative Example 3

[0117] The method for preparing the odor-free temperature-controlling microcapsules is the same as that in Example 1.

[0118] The auxiliary deodorant antioxidant 1500 and the above-mentioned deodorant temperature-controlling microcapsules are stirred at a temperature of 45°C and a speed of 300 rpm for 1 hour to obtain a deodorant temperature-controlling asphalt additive. The mass ratio of the auxiliary deodorant to the deodorant temperature-controlling microcapsules is 1:1.

[0119] Heat 50 parts by mass of base asphalt to 143°C, add 4 parts by mass of odor-free temperature-controlling asphalt additive at a rotation speed of 500 rpm, and stir for 4 hours to obtain odor-free temperature-controlling asphalt.

[0120] Comparative Example 4

[0121] When preparing the odor-free temperature-controlling microcapsules, steps S5-S7 are omitted, and steps S1-S4 are the same as in Example 1 to obtain a solid powder.

[0122] The auxiliary deodorant antioxidant 1500 was added to dodecyl dimethyl betaine, and the mixture was stirred at 300 rpm for 3 hours at a temperature of 45°C, and then the solid powder prepared by S4 was added, and the mixture was stirred for 1 hour to obtain a deodorant temperature-controlling asphalt additive. The mass ratio of the auxiliary deodorant, the solid powder prepared by S4, and the dodecyl dimethyl betaine was 1:1:1.

[0123] Heat 50 parts by mass of base asphalt to 143°C, add 6 parts by mass of odor-free temperature-controlling asphalt additive at a rotation speed of 500 rpm, and stir for 4 hours to obtain odor-free temperature-controlling asphalt.

[0124] Comparative Example 5

[0125] S1: Add n-docosane to a container, heat to melt at 50°C, then add formamide and hexadecyltrimethylammonium bromide, the mass ratio of n-docosane, hexadecyltrimethylammonium bromide and formamide is 4:1:50, and stir at 50°C and 400 rpm for 5 hours;

[0126] S2: adding tetraethyl orthosilicate to the reaction system of step S1, wherein the mass ratio of n-docosane to tetraethyl orthosilicate is 1:1, and continuing to stir at 400 rpm at 50° C. for 5 hours to obtain a Pickering emulsion;

[0127] S3: Use a peristaltic pump to slowly add 10 wt % dilute hydrochloric acid to the reaction system of step S2 until the pH of the reaction system is 4, continue stirring at 400 rpm at 50° C. for 5 hours, then stop stirring, keep the temperature unchanged and age for 24 hours, then filter and wash the solid powder in the reaction system, and vacuum dry it at -30° C. for 5 hours;

[0128] S4: adding the solid powder obtained in step S3 to a Tris buffer solution with a pH value of 8.5, wherein the mass ratio of the Tris buffer solution to the solid powder is 50:1, then adding dopamine hydrochloride to make the concentration of dopamine in the reaction system 4 mg / mL, stirring at a speed of 200 rpm at 25° C. for 12 hours, then stopping stirring, filtering and washing the bottom solid powder, and vacuum drying at a temperature of -30° C. for 5 hours;

[0129] S5: Manually stir the smoke suppressant compounds of equal mass ratio: 2-methylundecanal, 10-undecanal, carvone, 3-hydroxy-2-butanone, and then add the solid powder prepared in S4, anhydrous ethanol, and KOH, the mass ratio of the solid powder prepared in S4, the smoke suppressant compound, anhydrous ethanol, and KOH is 1:20:40:1, and further react under heating reflux conditions at 90°C for 6 hours, then filter and wash the bottom solid powder, and vacuum dry it at a temperature of -30°C for 5 hours;

[0130] S6: Ultrasonic dispersion of the solid powder obtained in step S5 in a 50wt% anhydrous copper sulfate-formamide solution, wherein the mass ratio of the solid powder to the anhydrous copper sulfate-formamide solution is 1:30, and the mixture is stirred at 400 rpm and 140°C for 2 hours. After the reaction is completed, the bottom solid powder is filtered and washed, and vacuum dried at -30°C for 5 hours to obtain odor-free temperature-controlling microcapsules.

[0131] The auxiliary deodorant antioxidant 1500 was added to dodecyl dimethyl betaine, and the mixture was stirred at 300 rpm for 3 hours at a temperature of 45°C, and then the deodorant temperature control microcapsules were added, and the mixture was stirred for 1 hour to obtain the deodorant temperature control asphalt additive. The mass ratio of the auxiliary deodorant, the deodorant temperature control microcapsules, and the dodecyl dimethyl betaine was 1:1:1.

[0132] Heat 50 parts by mass of base asphalt to 143°C, add 6 parts by mass of odor-free temperature-controlling asphalt additive at a rotation speed of 500 rpm, and stir for 4 hours to obtain odor-free temperature-controlling asphalt.

[0133] Comparative Example 6

[0134] The auxiliary deodorant antioxidant 1500 is added to dodecyl dimethyl betaine, and the mixture is stirred and mixed at a speed of 300 rpm for 3 hours at a temperature of 45°C to obtain a deodorant temperature-controlling asphalt additive. The mass ratio of the auxiliary deodorant to dodecyl dimethyl betaine is 1:1.

[0135] Heat 50 parts by mass of base asphalt to 143°C, add 4 parts by mass of odor-free temperature-controlling asphalt additive at a rotation speed of 500 rpm, and stir for 4 hours to obtain odor-free temperature-controlling asphalt.

[0136] Test Example 1

[0137] Sulfide is the main reason for the pungent odor of asphalt flue gas. Sinopec Donghai Brand No. 70 Grade A asphalt was used to prepare odor-free temperature-controlled asphalt. The odor-free temperature-controlled asphalt prepared in the embodiment and the comparative example was stored at 143°C for 0 day and 14 days. Then, an equal mass of the stored asphalt was transferred to a closed container, and flue gas was enriched at a temperature of 163°C and a stirring speed of 300 rpm for 4 hours. After the enrichment was completed, the gas in the closed container was aspirated, and the sulfide content in the gas was tested using gas chromatography. The obtained data are shown in Table 1 below.

[0138] Table 1 Gas chromatography sulfide test data

[0139]

[0140] Test Example 2

[0141] 100g of the odorless temperature-controlled asphalt sample obtained in Example 1 and Comparative Example 6 and the matrix asphalt were respectively injected into 100mL beakers, and then the sensor probe of the multi-channel temperature acquisition recorder was inserted into the middle of the asphalt system. After the asphalt was cooled for 24 hours, the beaker was moved into a 60°C water bath thermostat to record the temperature change of the asphalt system. The data obtained are shown in the attached figure. Figure 2 shown.

Claims

1. A clean and temperature-controlling asphalt additive, characterized in that: The following components are included by weight: Odor-free temperature-control microcapsules, 1-5 portions; Auxiliary deodorant, 1-5 parts; Dispersant, 1-5 parts; The odor-free temperature-controlling microcapsule comprises a composite shell material and a core material, wherein the composite shell material comprises silicon dioxide / nano-tourmaline / polydopamine, the core material comprises normal alkanes with a phase transition temperature of 40-60°C, and the surface of the composite shell material is loaded with metal chelates and smoke-suppressing compounds containing active α-H.

2. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The auxiliary deodorant is selected from one or more phosphite antioxidants with a boiling point greater than 220°C; the phosphite antioxidant with a boiling point greater than 220°C is selected from one or more of tris(2,4-di-tert-butylphenyl) phosphite, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphospiro[5.5]undecane, tris(nonylphenol) phosphite, antioxidant 1500 (4,4'-isopropyl diphenyl C12-15-ol phosphite), and distearyl pentaerythritol diphosphite.

3. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The dispersant is selected from one or more of dodecyl dimethyl betaine and 1-hydroxyethyl-carboxymethyl-alkyl imidazoline.

4. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The particle size of the odor-free temperature-controlling microcapsule is 1-5 μm.

5. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The mass ratio of the composite shell material to the core material of the odor-free temperature-controlling microcapsule is 1:(0.5-2).

6. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The composite shell material of the odor-free temperature-controlling microcapsule comprises silicon dioxide / nano-tourmaline / polydopamine, wherein the mass ratio of silicon dioxide to nano-tourmaline is (1-5):1, and the mass ratio of silicon dioxide to polydopamine is 1:(0.1-0.5).

7. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The normal alkane with a phase transition temperature of 40-60° C. is one or more of n-octadecane, n-eicosane, and n-docosane, preferably n-docosane.

8. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The surface of the composite shell material is loaded with a metal chelate, wherein the metal is preferably copper.

9. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The shell material surface is loaded with metal chelates and smoke suppressant compounds containing active α-H, the metal loading accounts for 0.1wt%-15wt% of the total mass of the odor-free temperature-controlling microcapsules; the smoke suppressant compounds containing active α-H account for 0.1wt%-20wt% of the total mass of the odor-free temperature-controlling microcapsules.

10. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The smoke suppressant compound containing active α-H is selected from one or more of aldehyde compounds having a carbon number greater than 9 or ketone compounds having a carbon number greater than 8; Preferably, the aldehyde compound having a carbon number greater than 9 is selected from one or more of o-methylcinnamaldehyde, p-methylcinnamaldehyde, anisaldehyde, 2-methylundecanal, 10-undecanal, ethyl vanillin, benzaldehyde, phenylacetaldehyde, p-hydroxybenzaldehyde, butylphenylmethylpropionaldehyde, neral, hydroxymethylpentylcyclohexene acetal, 3-(4-ethylphenyl)-2,2-dimethylpropionaldehyde, vanillin propanediol acetal, methylhexylcinnamaldehyde, methylpentylcinnamaldehyde, and diethylaminobenzaldehyde; Preferably, the ketone compound having a carbon number greater than 8 is selected from one or more of carvone, 3-hydroxy-2-butanone, 2,3-butanedione 3-pentene-2-one, and 6-methyl-3,5-heptadien-2-one.

11. The odorless temperature-controlling asphalt additive according to claim 1, characterized in that: The preparation method of the odor-free temperature-controlling microcapsule comprises the following steps: S1: mixing nano-tourmaline, a surfactant and a solvent, modifying the mixture under stirring, washing the mixture after the modification, and freeze-drying the mixture to obtain modified nano-tourmaline; S2: heating the core material raw material until it is melted, then adding the solvent and the modified nano-tourmaline obtained in step S1, and stirring and mixing; S3: adding a silicon dioxide precursor to the reaction system in step S2, stirring and mixing, and obtaining a Pickering emulsion; S4: adjusting the pH value of the Pickering emulsion obtained in step S3 to 2-5, stirring and then aging, filtering, washing, and freeze-drying; S5: adding the solid powder obtained in step S4 to a buffer solution, adding dopamine hydrochloride, treating under stirring, and then filtering, washing, and freeze-drying; S6: adding the solid powder obtained in step S5, the smoke suppressant compound containing active α-H, and a strong base to an organic solvent, reacting under heating reflux conditions, cooling, filtering, washing, and freeze-drying; S7: ultrasonically dispersing the solid powder obtained in step S6 in a metal ion salt-formamide solution, reacting under stirring, and after the reaction is completed, filtering, washing, and freeze-drying to obtain odor-free temperature-controlling microcapsules.

12. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S1, the surfactant is a cationic surfactant, preferably at least one of hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, 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, 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 (5-50):

1.

13. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S1, the stirring speed is 200-500 rpm; the modification temperature is 100-190° C., and the modification time is 2-5 hours; And / or, in step S2, the stirring speed is 400-600 rpm, the stirring temperature is 40-60° C., and the stirring time is 4-6 hours; And / or, in step S3, the stirring speed is 400-600 rpm, the stirring temperature is 40-60° C., and the stirring time is 4-6 hours; And / or, in step S4, the stirring speed is 400-600 rpm, the stirring temperature is 40-60° C., and the stirring time is 4-6 hours; And / or, in step S5, the stirring speed is 100-300 rpm, the stirring temperature is 20-40° C., and the stirring time is 12-24 hours; And / or, in step S7, the stirring speed is 200-450 rpm, the reaction temperature is 100-190° C., and the reaction time is 2-5 hours.

14. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S2, 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, in step S2, the mass ratio of the core material raw material to the modified nano-tourmaline is (1-10):1, and the mass ratio of the solvent to the modified nano-tourmaline is (20-80):

1.

15. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S3, the silicon dioxide precursor is a silicate compound, preferably at least one of methyl silicate, ethyl orthosilicate, tetraethyl orthosilicate, and butyl orthosilicate, and more preferably ethyl orthosilicate; And / or, the mass ratio of the core material raw material to the silica precursor is (0.5-1.5):

1.

16. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S5, the buffer solution is one or more of a phosphate buffer solution, a carbonate buffer solution, and a tris(hydroxymethyl)aminomethane hydrochloride buffer solution, preferably a tris(hydroxymethyl)aminomethane hydrochloride buffer solution; the pH value of the buffer solution is preferably 8-10; And / or, the mass ratio of the buffer solution to the solid powder obtained in step S4 is (10-100):

1.

17. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S5, after adding dopamine hydrochloride, the mass concentration of dopamine in the reaction system is 2-10 mg / mL.

18. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S6, the organic solvent is selected from one or more of methanol, butanediol, ethylene glycol, n-butanol, and anhydrous ethanol, preferably anhydrous ethanol; And / or, in step S6, the mass ratio of the solid powder obtained in step S5 to the smoke suppressant compound containing active α-H is 1:(10-40); the mass ratio of the solid powder obtained in step S5 to the organic solvent is 1:(20-80); the mass ratio of the solid powder obtained in step S5 to the strong base is 1:(0.5-2); And / or, in step S6, the strong base is one of solid KOH and solid NaOH, preferably solid KOH; And / or, in step S6, the reaction conditions of heating reflux are: reaction temperature is 80-220° C., and reaction time is 5-10 hours.

19. The odorless temperature-controlling asphalt additive according to claim 11, characterized in that: In step S7, the metal ion salt is preferably a copper ion salt, and more preferably anhydrous copper sulfate; And / or, the mass ratio of the metal ion salt-formamide solution to the solid powder obtained in step S6 is (5-30):

1.

20. A odorless temperature-controlling asphalt comprising the following components by weight: Base asphalt, 50-500 parts; 1-50 parts of the odorless temperature-controlling asphalt additive according to any one of claims 1-19.

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