A clean asphalt and a method for preparing the same
By encapsulating active components with organic and inorganic microcapsules, the problem of flue gas release during asphalt pavement construction has been solved, achieving slow release and long-term action of active components, thus reducing environmental pollution and health risks.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-12-05
- Publication Date
- 2026-06-05
AI Technical Summary
In existing technologies, the release of asphalt fumes during asphalt pavement construction is difficult to control, leading to environmental pollution and health risks. Furthermore, the active components have poor compatibility and short action time.
The active components are encapsulated using organic and inorganic microcapsules. By adjusting the capsule wall thickness and material selection, the active components are slowly released and act for a long time. Combined with antioxidants, this reduces asphalt fume emissions.
It effectively reduces asphalt fume emissions, prolongs the action time of active components, improves compatibility with asphalt, and reduces the risk of environmental pollution.
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Figure BDA0005172712260000151
Abstract
Description
Technical Field
[0001] This invention relates to a special type of asphalt and its preparation method, and particularly to a purified asphalt and its preparation method. Background Technology
[0002] As a major type of highway, asphalt pavement still uses the traditional hot-mix hot-paving process in its construction. During construction, asphalt comes into contact with oxygen in the air and reacts: on the one hand, it undergoes a condensation reaction to generate polycyclic aromatic hydrocarbons with larger molecular weights, which further condense into gums and asphaltenes; on the other hand, asphalt molecules will decompose under heating conditions to generate compounds with smaller molecular weights. These small molecule compounds volatilize and form asphalt fumes, which seriously disrupt the ecological balance, pollute the surrounding environment, and harm human health.
[0003] Given that volatile organic compounds (VOCs) are released unorganized during the paving process of asphalt pavement, and it is difficult to collect and treat them throughout the entire process, exploring how to reduce the release of asphalt fumes at the source, achieve clean construction of asphalt pavement, and ensure the harmonious development of the transportation industry and the social economy is an urgent problem to be solved.
[0004] CN101842426A discloses a method for reducing the odor of asphalt-like substances. This method reduces the odor of asphalt-like substances by adding activators and diluents. However, the added activators have poor reactivity and limited action time, making them unable to work for a long time. CN109749466A discloses a smoke suppressant and odor deodorizer additive, its preparation method, and modified asphalt. It reduces the emission of asphalt fumes by using metal-organic framework compounds, inorganic adsorbents, reactive odor inhibitors, and free radical scavengers. However, its inorganic adsorbents have poor compatibility with asphalt, affecting the performance of asphalt. It also suffers from the problem of short action time of the active components.
[0005] In summary, existing technologies simply add inorganic fillers or active components to asphalt, which leads to segregation and stratification of the inorganic fillers and asphalt, as well as the limited action time of the active components, preventing them from exerting their effects for an extended period. Summary of the Invention
[0006] To address the shortcomings of existing technologies, this invention provides a purified asphalt and its preparation method. The purified asphalt of this invention can effectively reduce asphalt fume emissions, reduce environmental pollution, and achieve the slow release of active components, prolonging their action time, while also exhibiting excellent compatibility with asphalt.
[0007] This invention provides a purified asphalt, comprising the following raw material components by weight:
[0008] Asphalt: 100 parts
[0009] Organic microcapsules: 0.05–0.2 parts;
[0010] Inorganic microcapsules: 0.05–0.2 parts;
[0011] Antioxidant: 0.01–0.1 parts;
[0012] The organic microcapsule includes a core, a wall, and a membrane encapsulation material, wherein the wall encapsulates the outer layer of the core, and the membrane encapsulation material encapsulates the outer layer of the wall; the core includes a first active component, the wall includes resin, and the membrane encapsulation material includes rubber material.
[0013] Furthermore, the elastic modulus of the organic microcapsule and the sum of the thicknesses of the capsule wall and the membrane encapsulation material satisfy the following formula:
[0014] Y = 0.42X 2 -0.92X+T;
[0015] Wherein, Y is the elastic modulus of the organic microcapsule, in GPa; X is the sum of the thicknesses of the capsule wall and the membrane encapsulation material, in μm; and T is 1 ± 0.1.
[0016] Furthermore, the elastic modulus of the organic microcapsule was obtained by testing the mechanical properties of the organic microcapsule using a nanoindenter, and the thickness of the capsule wall and membrane encapsulation material was obtained by testing the frozen sections of the organic microcapsule using a scanning electron microscope.
[0017] Furthermore, in the organic microcapsule, the sum of the thickness of the capsule wall and the membrane encapsulation material is 0.2–8 μm, preferably 0.5–5 μm.
[0018] Furthermore, the mass ratio of the core, wall, and membrane encapsulation material in the organic microcapsule is 1:
[0019] (0.7~1): (0.2~0.3).
[0020] Furthermore, the size of the organic microcapsule conforms to the size of conventional microcapsules in the art, generally below 50 micrometers, preferably below 20 micrometers, and more preferably 3 to 15 μm.
[0021] Furthermore, in the organic microcapsule, the first active component is one or more of aldehyde compounds and ketone compounds. The aldehyde compounds are selected from one or more of p-methylbenzaldehyde, decanal, o-carboxybenzaldehyde, p-isopropylbenzaldehyde, cinnamaldehyde, p-hydroxybenzaldehyde, p-methoxybenzaldehyde, 2-methyl-3-(3,4-methylene-dioxyphenyl)propanal, 3,4-methylenedioxybenzaldehyde, 3-(4-isopropylphenyl)-2-methylpropanal, ethyl vanillin, phenylacetaldehyde, anisaldehyde, nonadien-2,6-aldehyde, 2,6-dimethyl-2,6-octadienal, vanillin, citronellol, neraldehyde, hydroxymethylpentylcyclohexene acetal, p-diethylaminobenzaldehyde, and undecenal; the ketone compounds are selected from one or more of 6-methyl-3,5-heptadien-2-one, 2-undecenone, acetophenone, ionone, irisone, methyl ionone, damasone, and dihydrodamasone.
[0022] Furthermore, the capsule wall is made of melamine resin.
[0023] Furthermore, the membrane wrapping material is a uniform and dense membrane material.
[0024] Furthermore, the rubber material is at least one of chlorinated rubber, styrene-butadiene rubber, and chloroprene rubber.
[0025] Furthermore, the inorganic microcapsule includes a core and a wall, wherein the wall wraps around the core; the core includes a second active component, and the wall includes organosilane-modified silica.
[0026] Furthermore, the mass ratio of the capsule core to the capsule wall in the inorganic microcapsule is 1:(0.3-0.5).
[0027] Furthermore, the size of the inorganic microcapsule conforms to the size of conventional microcapsules in the art, generally below 50 micrometers, preferably below 20 micrometers, and more preferably 1 to 15 μm.
[0028] Further, in the inorganic microcapsules, the second active component is one or more ester compounds. The ester compounds are selected from one or more of the following: methyl salicylate, methyl cinnamate, ethyl cinnamate, ethyl phenylacetate, methyl phenylacetate, geraniol phenylacetate, phenethyl phenylacetate, isoamyl phenylacetate, benzyl salicylate, p-methylbenzyl acetate, benzyl acetate, isobutyl benzoate, isoamyl salicylate, benzyl cinnamate, phenethyl cinnamate, linaloyl formate, linaloyl acetate, linaloyl isobutyrate, menthyl acetate, terpineol acetate, and borneol acetate.
[0029] Furthermore, in the inorganic microcapsules, the organosilane is a sulfonylsilane obtained by oxidizing mercaptosilane. The mercaptosilane is one or more of γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane.
[0030] Furthermore, the antioxidant is an antioxidant with a carboxyl group, preferably one or more of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid, 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid, 3-(3,5-dimethoxy-4-hydroxyphenyl)acrylic acid, and 3-(3-methoxy-4-hydroxyphenyl)acrylic acid.
[0031] Furthermore, the asphalt can be at least one of straight-run asphalt, polymer-modified asphalt, and natural asphalt. Preferably, the asphalt has a penetration of 30–210 1 / 10 mm at 25°C.
[0032] The present invention also provides a method for preparing purified asphalt as described above, comprising:
[0033] Organic microcapsules and inorganic microcapsules were prepared separately, and then mixed evenly with antioxidants and asphalt under heating conditions to obtain purified asphalt.
[0034] Furthermore, the method for preparing the purified asphalt includes:
[0035] (1) Mix the first active component, the first emulsifier and water to form an oil-in-water emulsion;
[0036] (2) The water-in-oil emulsion is reacted with the resin prepolymer, and then filtered, washed and dried to obtain the pre-coated material;
[0037] (3) In the presence of a volatile solvent, the rubber material is mixed with the pre-coated material obtained in step (2), and then the resulting mixture is mixed with water and heated until the volatile solvent evaporates to obtain organic microcapsules;
[0038] (4) The second active component, the second emulsifier and water are mixed and reacted with the silicon source. Then, the mixture is washed, filtered and dried to obtain silica microcapsules coated with the active component.
[0039] (5) The silica microcapsules coated with the active components, organosilane and organic solvent are mixed and surface modification reaction is carried out. Then, after cooling, filtration, washing and drying, surface-modified silica microcapsules are obtained.
[0040] (6) After mixing the surface-modified silica microcapsules with hydrogen peroxide solution for oxidation reaction, the microcapsules are washed and dried to obtain inorganic microcapsules.
[0041] (7) The organic microcapsules, inorganic microcapsules and antioxidants are added to the asphalt and mixed evenly under heating conditions to obtain purified asphalt.
[0042] Further, in step (1), the weight ratio of the first active component, the first emulsifier, and water is 1:(0.05~0.09):(6~9).
[0043] Further, in step (1) or step (4), the first emulsifier and the second emulsifier are each independently selected from one or more of sodium stearate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyldimethylhydroxyethylammonium chloride, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and hexadecane polyoxyethylene ether.
[0044] Furthermore, in step (1), the mixing process can be carried out in a shearing machine, and the shearing operation conditions may include: a rotation speed of 2000 to 4000 r / min and a time of 20 to 30 min.
[0045] Further, the preferred operation process of step (1) is to dissolve the first active component in water (the water temperature is preferably 60-90°C), then add the emulsifier and perform high-speed shear emulsification.
[0046] Further, in step (2), before the oil-in-water emulsion reacts with the resin prepolymer, the pH value of the oil-in-water emulsion is adjusted to below 5, preferably to 2-4. The reagent used to adjust the pH value can be a conventional inorganic acid solution, such as dilute hydrochloric acid.
[0047] Further, in step (2), the weight ratio of the oil-in-water emulsion to the resin prepolymer is 1:(0.08~0.15).
[0048] Further, in step (2), the reaction between the oil-in-water emulsion and the resin prepolymer is carried out under stirring. The stirring speed can be 400-1000 r / min, the reaction temperature can be 60-90℃, and the time can be 1-5 h.
[0049] Further, in step (2), the resin prepolymer is preferably a melamine resin prepolymer, which can be prepared by the following method:
[0050] Melamine and formaldehyde solutions are mixed and dissolved in water, and the pH value is adjusted to 7.5-9.5. Then, the mixture is placed in a constant temperature water bath at 60-90℃ and reacted with stirring for 0.5-3.5 hours.
[0051] Furthermore, the formaldehyde solution has a mass concentration of 30% to 40%. The weight ratio of melamine, formaldehyde solution, and water is 1:(2 to 3):(8 to 10).
[0052] Furthermore, in step (2), the washing process may include washing with water and ethanol two or more times respectively.
[0053] Furthermore, in step (2), the drying process can be carried out in an oven, and the drying temperature can be 60-90°C for 5-10 hours.
[0054] Further, in step (3), the weight ratio of the rubber material to the pre-coated material obtained in step (2) is (0.1~0.2):1.
[0055] Furthermore, in step (3), the heating is carried out under stirring, and the stirring speed can be 400-1000 r / min.
[0056] Furthermore, in step (3), the volatile solvent is selected from one or more of carbon tetrachloride, dichloromethane, and trichloroethylene.
[0057] Further, in step (3), the weight ratio of the rubber material, volatile solvent, and water is 1:(10-20):(50-150).
[0058] Furthermore, in step (4), the silicon source is preferably tetraethyl orthosilicate.
[0059] Further, the preferred procedure in step (4) is as follows: dissolve the second active component in water (preferably at a temperature of 60–80°C), then add the second emulsifier, perform high-speed shear emulsification, adjust the pH, and then add a silicon source for reaction. Further, the shearing conditions may include: a rotation speed of 2000–4000 r / min and a time of 20–30 min. Further, the pH adjustment value is 2.5–5. The pH adjustment can be achieved using commonly used acid-base regulators in the art, such as hydrochloric acid.
[0060] Further, in step (4), the weight ratio of the second active component, the second emulsifier, water, and silicon source is 1:(0.05~0.3):(3~7):(1~5), preferably 1:(0.1~0.2):(4~5):(1~1.5).
[0061] Furthermore, in step (4), the reaction conditions are: reaction time of 10-18h and reaction temperature of 60-80℃.
[0062] Furthermore, in step (4), the washing and filtering are performed using conventional methods in the art. The drying temperature can be 80–100°C, and the time can be 5–8 hours.
[0063] Further, in step (5), the weight ratio of the silica microcapsules coated with the active components to the organosilane and the organic solvent is 1:(0.01-0.1):(10-30).
[0064] Furthermore, in step (5), the organic solvent is preferably one or more of xylene, toluene, cyclohexanone, chlorobenzene and pyridine.
[0065] Furthermore, in step (5), the surface modification reaction is carried out at a temperature of 100℃ to 120℃ for a time of 1 to 3 hours.
[0066] Furthermore, in step (5), the filtration, washing, and drying can all be performed using conventional methods in the art. The washing can be done using solvents such as ethanol, chloroform, and acetone, and the drying is performed by allowing the solvent to evaporate. The drying temperature can be 80℃~120℃, and the time can be 0.5~5h.
[0067] Further, in step (6), the weight ratio of the surface-modified silica microcapsules to the hydrogen peroxide solution is 1:(5-10). The mass fraction of the hydrogen peroxide solution is 10%-30%.
[0068] Furthermore, in step (6), the oxidation reaction is carried out at a temperature of 50–90°C for 1–5 hours.
[0069] Furthermore, in step (6), the washing process preferably involves washing with water and ethanol two or more times respectively. The drying temperature is 60–90°C, and the drying time is 6–10 hours.
[0070] Further, in step (7), the heating temperature is 140-180°C, and the mixing can be done by mechanical stirring; preferably, the stirring speed is 500-1000 r / min, and the stirring time is 1-3 h.
[0071] Compared with the prior art, the purified asphalt and its preparation method of the present invention have the following advantages:
[0072] This invention employs organic microcapsules, wherein the core comprises a first active component, the capsule wall comprises resin, and the membrane encapsulation material comprises rubber. The overall design ensures both sufficient strength and effective integration with asphalt, exhibiting excellent compatibility. The inorganic microcapsules used in this invention have an outer surface modified with organosilanes, demonstrating excellent compatibility with asphalt.
[0073] The organic microcapsules used in this invention have an elastic modulus that satisfies a specific functional relationship with the thickness of the capsule wall. In practical applications, the elastic modulus of the microcapsules can be controlled within the required parameter range by adjusting the thickness of the capsule wall.
[0074] This invention employs organic and inorganic microcapsules to encapsulate different active components, enabling slow release and stepwise reactions of the active components, extending their action time, and resulting in cleaner asphalt with longer storage and service life. Simultaneously, the organosilane on the outer surface of the inorganic microcapsules contains sulfonic acid groups, and the antioxidant contains carboxyl groups, which can effectively catalyze the reaction between the active components and toxic and harmful substances in the asphalt, effectively reducing asphalt fume emissions and minimizing environmental pollution. Detailed Implementation
[0075] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.
[0076] In this invention, the elastic modulus of the microcapsule is obtained by testing the mechanical properties of the microcapsule using a nanoindenter (KLA Corporation iNano), and the thickness of the capsule wall is obtained by testing the frozen sections of the microcapsule using a scanning electron microscope (Hitachi S-4800).
[0077] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.
[0078] Example 1
[0079] (1) Add 1 part by weight of decanal to 9 parts by weight of water at 70°C, then add 0.06 parts by weight of hexadecyltrimethylammonium bromide, and shear emulsify using a shear machine at 2200 r / min for 20 min to form an oil-in-water emulsion in the aqueous phase.
[0080] (2) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt% and 8 parts by weight of deionized water in a three-necked flask, adjust the pH value to 7.5, and then place it in a constant temperature water bath at 60℃ and stir at 800 r / min for 0.5 h to obtain melamine resin prepolymer.
[0081] Add dilute hydrochloric acid dropwise to 1 part by weight of oil-in-water emulsion to adjust the pH value to 2.5. Slowly add 0.1 parts by weight of the prepared melamine resin prepolymer to the oil-in-water emulsion, stir at 700 r / min, and react at 75°C for 2 h. After the reaction is completed, filter the resulting mixed solution, wash twice with water and ethanol respectively, and dry in an oven at 60°C for 10 h to obtain the pre-coated material.
[0082] (3) Dissolve 0.14 parts by weight of chlorinated rubber in 1.8 parts by weight of dichloromethane, add 1 part by weight of the pre-coated material, and mix thoroughly. Add the resulting mixture to 15 parts by weight of water, stir at 400 r / min, and raise the temperature until the solvent evaporates to obtain organic microcapsules.
[0083] The elastic modulus of the organic microcapsules was measured to be 1.6 GPa using a nanoindenter. Scanning electron microscopy was used to measure the combined thickness of the capsule wall and membrane encapsulation material in frozen sections of the microcapsules, which was found to be 2.7 μm, consistent with the calculation formula Y = 0.42X. 2 -0.92X+T. Testing revealed that the mass ratio of the core, wall, and membrane encapsulation material in this organic microcapsule was 1:1:0.27. The size of the organic microcapsule was 7–8 μm.
[0084] (4) Add 1 part by weight of ethyl phenylacetate to 5 parts by weight of water at 60℃, add 0.1 part by weight of hexadecyltrimethylammonium bromide, shear emulsify using a shear machine at 2000 r / min for 30 min, adjust the pH value to 2.5, add 1.5 parts by weight of tetraethyl orthosilicate, react for 10 h, and then wash, filter, and dry at 80℃ for 8 h to obtain silica microcapsules coated with active components.
[0085] (5) 1 part by weight of silica microcapsules coated with active components and 0.01 part by weight of γ-mercaptopropyltrimethoxysilane were added to 10 parts by weight of toluene. The surface modification reaction was carried out at 100°C under reflux for 1 hour. After cooling, the surface was filtered and washed with ethanol and dried at 80°C for 5 hours to obtain surface-modified silica microcapsules.
[0086] (6) One part by weight of surface-modified silica microcapsules was added to five parts by weight of a 30% hydrogen peroxide solution. After oxidation at 50°C for 1 hour, the microcapsules were washed twice with water and twice with ethanol, and then dried at 60°C for 6 hours to obtain inorganic microcapsules. The mass ratio of the core to the wall in these inorganic microcapsules was found to be 1:0.43. The size of these inorganic microcapsules was 4–7 μm.
[0087] (7) Add 0.1 parts by weight of organic microcapsules, 0.05 parts by weight of inorganic microcapsules, and 0.1 parts by weight of 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid to 100 parts by weight of straight-run pitch (with a penetration of 70 at 25°C).
[0088] In 1 / 10mm), under heating conditions of 140℃ and stirring at 800r / min for 3h, clean asphalt is obtained.
[0089] Example 2
[0090] (1) Add 1 part by weight of citronellal to 7 parts by weight of water at 70°C, then add 0.06 parts by weight of nonylphenol polyoxyethylene ether, and emulsify by shearing at 2500 r / min for 30 min to form an oil-in-water emulsion in the aqueous phase.
[0091] (2) Dissolve 1 part by weight of melamine, 3 parts by weight of formaldehyde solution with a concentration of 37 wt% and 10 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 80℃ and stir at 600 r / min for 1 h to obtain melamine resin prepolymer.
[0092] Dilute hydrochloric acid was added dropwise to 1 part by weight of an oil-in-water emulsion to adjust the pH value to 3.5. 0.12 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the oil-in-water emulsion. The mixture was stirred at 600 r / min and reacted at 70 °C for 3 h. After the reaction was completed, the resulting mixed solution was filtered, washed twice with water and ethanol respectively, and dried in an oven at 70 °C for 8 h to obtain the pre-coated material.
[0093] (3) Dissolve 0.13 parts by weight of chloroprene rubber in 3 parts by weight of carbon tetrachloride, add 1 part by weight of the pre-coated material, and mix thoroughly. Add the resulting mixture to 10 parts by weight of water, stir at 500 r / min, and raise the temperature until the solvent evaporates to obtain organic microcapsules.
[0094] The elastic modulus of the organic microcapsules was measured to be 0.5 GPa using a nanoindenter. Scanning electron microscopy was used to measure the combined thickness of the capsule wall and membrane encapsulation material in frozen sections of the microcapsules, which was found to be 1.2 μm, consistent with the calculation formula Y = 0.42X. 2 -0.92X+T. Testing revealed that the mass ratio of the core, wall, and membrane encapsulation material in this organic microcapsule was 1:0.91:0.30. The size of the organic microcapsule was 4–6 μm.
[0095] (4) Add 1 part by weight of benzyl acetate to 5 parts by weight of water at 70°C, add 0.15 parts by weight of sodium stearate, shear emulsify at 3000 r / min for 30 min using a shearing machine, adjust the pH value to 4, add 1.4 parts by weight of tetraethyl orthosilicate, react for 12 h, wash and filter according to routine, and dry at 90°C for 8 h to obtain silica microcapsules coated with active components.
[0096] (5) 1 part by weight of silica microcapsules coated with active components and 0.03 parts by weight of γ-mercaptopropyltriethoxysilane were added to 10 parts by weight of toluene. The surface modification reaction was carried out at 100°C under reflux for 3 hours. After cooling, the surface was filtered and washed with ethanol and dried at 90°C for 5 hours to obtain surface-modified silica microcapsules.
[0097] (6) One part by weight of surface-modified silica microcapsules was added to six parts by weight of a 30% hydrogen peroxide solution. After oxidation at 80°C for 2 hours, the microcapsules were washed three times with water and three times with ethanol, and then dried at 70°C for 6 hours to obtain inorganic microcapsules. The mass ratio of the capsule core to the capsule wall in the inorganic microcapsules was found to be 1:0.41. The size of the inorganic microcapsules was 2–6 μm.
[0098] (7) Add 0.1 parts by weight of organic microcapsules, 0.1 parts by weight of inorganic microcapsules and 0.1 parts by weight of 3,5-di-tert-butyl-4-hydroxybenzoic acid to 100 parts by weight of SBS modified asphalt (penetration of 601 / 10mm at 25℃), and stir at 800r / min for 3h under heating conditions at 150℃ to obtain purified asphalt.
[0099] Example 3
[0100] (1) Add 1 part by weight of 2-undecanone to 6 parts by weight of water at 65°C, then add 0.09 parts by weight of octylphenol polyoxyethylene ether, and emulsify by shearing at 3000 r / min for 25 min to form an oil-in-water emulsion in the aqueous phase.
[0101] (2) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 9 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 70℃ and stir at 500 r / min for 2 h to obtain melamine resin prepolymer.
[0102] Dilute hydrochloric acid was added dropwise to 1 part by weight of an oil-in-water emulsion to adjust the pH to 2.5. 0.13 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the oil-in-water emulsion. The mixture was stirred at 500 r / min and reacted at 65 °C for 3 h. After the reaction was completed, the resulting mixed solution was filtered, washed twice with water and ethanol respectively, and dried in an oven at 90 °C for 6 h to obtain the pre-coated material.
[0103] (3) Dissolve 0.15 parts by weight of styrene-butadiene rubber in 3 parts by weight of dichloromethane, add 1 part by weight of the pre-coated material, and mix thoroughly. Add the resulting mixture to 18 parts by weight of water, stir at 600 r / min, and raise the temperature until the solvent evaporates to obtain organic microcapsules.
[0104] The elastic modulus of the organic microcapsules was measured to be 0.4 GPa using a nanoindenter. Scanning electron microscopy was used to measure the combined thickness of the capsule wall and membrane encapsulation material in frozen sections of the microcapsules, which was found to be 1.1 μm, consistent with the calculation formula Y = 0.42X. 2 -0.92X+T. Testing revealed that the mass ratio of the core, wall, and membrane encapsulation material in this organic microcapsule was 1:0.89:0.28. The size of the organic microcapsule was 4–6 μm.
[0105] (4) Add 1 part by weight of ethyl cinnamate to 4 parts by weight of water at 65°C, add 0.1 part by weight of sodium dodecylbenzenesulfonate, shear emulsify at 2000 r / min for 20 min using a shearing machine, adjust the pH value to 5, add 1.3 parts by weight of tetraethyl orthosilicate, react for 14 h, wash and filter according to routine, and dry at 100°C for 6 h to obtain silica microcapsules coated with active components.
[0106] (5) 1 part by weight of silica microcapsules coated with active components and 0.05 parts by weight of γ-mercaptopropyltrimethoxysilane were added to 15 parts by weight of toluene. The surface modification reaction was carried out at 110°C under reflux for 2 hours. After cooling, the surface was filtered and washed with ethanol and dried at 90°C for 4 hours to obtain surface-modified silica microcapsules.
[0107] (6) One part by weight of surface-modified silica microcapsules was added to eight parts by weight of a 30% hydrogen peroxide solution. After oxidation at 80°C for 1 hour, the microcapsules were washed twice with water and ethanol, respectively, and dried at 60°C for 8 hours to obtain inorganic microcapsules. The mass ratio of the capsule core to the capsule wall in the inorganic microcapsules was found to be 1:0.37. The size of the inorganic microcapsules was 3–6 μm.
[0108] (7) 0.2 parts by weight of organic microcapsules, 0.1 parts by weight of inorganic microcapsules and 0.01 parts by weight of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid were added to 100 parts by weight of natural asphalt (penetration of 501 / 10mm at 25℃), and stirred at 500r / min for 2h under heating conditions at 160℃ to obtain purified asphalt.
[0109] Example 4
[0110] (1) Add 1 part by weight of methyl ionone to 6 parts by weight of water at 80°C, then add 0.06 parts by weight of sodium dodecylbenzenesulfonate, and emulsify by shearing at 3500 r / min for 20 min to form an oil-in-water emulsion in the aqueous phase.
[0111] (2) Dissolve 1 part by weight of melamine, 3 parts by weight of formaldehyde solution with a concentration of 37 wt.% and 9 parts by weight of deionized water in a three-necked flask, adjust the pH value to 9.5, and then place it in a constant temperature water bath at 60℃ and stir at 700 r / min for 2 h to obtain melamine resin prepolymer.
[0112] Dilute hydrochloric acid was added dropwise to 1 part by weight of an oil-in-water emulsion to adjust the pH to 3.5. 0.11 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the oil-in-water emulsion. The mixture was stirred at 500 r / min and reacted at 60 °C for 5 h. After the reaction was completed, the resulting mixed solution was filtered, washed twice with water and ethanol respectively, and dried in an oven at 90 °C for 6 h to obtain the pre-coated material.
[0113] (3) Dissolve 0.15 parts by weight of chlorinated rubber in 1.7 parts by weight of dichloromethane, add 1 part by weight of the pre-coating material, and stir thoroughly. Add the resulting mixture to 18 parts by weight of water, stir at 700 r / min, and raise the temperature until the solvent evaporates, so that the chlorinated rubber gradually forms a film and adheres to the outer wall of the inner wall coating repair material to obtain organic microcapsules.
[0114] The elastic modulus of the organic microcapsules was measured to be 0.6 GPa using a nanoindenter. Scanning electron microscopy was used to measure the combined thickness of the capsule wall and membrane encapsulation material in frozen sections of the microcapsules, which was found to be 0.7 μm, consistent with the calculation formula Y = 0.42X. 2 -0.92X+T. Testing revealed that the mass ratio of the core, wall, and membrane encapsulation material in this organic microcapsule was 1:0.77:0.26. The size of the organic microcapsule was 3–5 μm.
[0115] (4) Add 1 part by weight of linaloate formate to 3.5 parts by weight of water at 70°C, add 0.2 parts by weight of nonylphenol polyoxyethylene ether, shear emulsify by shearing at 3000 r / min for 30 min, adjust the pH to 3.5, add 1.2 parts by weight of tetraethyl orthosilicate, react for 18 h, wash and filter according to routine, dry at 85°C for 7 h to obtain silica microcapsules coated with active components.
[0116] (5) 1 part by weight of silica microcapsules coated with active components and 0.08 parts by weight of γ-mercaptopropylmethyldiethoxysilane were added to 20 parts by weight of toluene. The surface modification reaction was carried out at 100°C under reflux for 2 hours. After cooling, the surface was filtered and washed with ethanol and dried at 120°C for 4 hours to obtain surface-modified silica microcapsules.
[0117] (6) One part by weight of surface-modified silica microcapsules was added to eight parts by weight of a 30% hydrogen peroxide solution. After oxidation at 60°C for 4 hours, the microcapsules were washed three times with water and three times with ethanol, and then dried at 90°C for 6 hours to obtain inorganic microcapsules. The mass ratio of the capsule core to the capsule wall in the inorganic microcapsules was found to be 1:0.33. The size of the inorganic microcapsules was 2–5 μm.
[0118] (7) 0.15 parts by weight of organic microcapsules, 0.15 parts by weight of inorganic microcapsules and 0.1 parts by weight of 3-(3,5-dimethoxy-4-hydroxyphenyl)acrylic acid were added to 100 parts by weight of straight-run pitch (penetration of 70 1 / 10 mm at 25°C) and stirred at 1000 r / min for 2 h under heating conditions at 150°C to obtain purified pitch.
[0119] Example 5
[0120] (1) Add 1 part by weight of p-diethylaminobenzaldehyde to 6 parts by weight of water at 80°C, then add 0.08 parts by weight of cetyltrimethylammonium chloride, and emulsify by shearing at 4000 r / min for 30 min to form an oil-in-water emulsion in the aqueous phase.
[0121] (2) Dissolve 1 part by weight of melamine, 2 parts by weight of formaldehyde solution with a concentration of 37 wt% and 9 parts by weight of deionized water in a three-necked flask, adjust the pH value to 8.5, and then place it in a constant temperature water bath at 90℃ and stir at 400 r / min for 3.5 h to obtain melamine resin prepolymer.
[0122] Dilute hydrochloric acid was added dropwise to 1 part by weight of an oil-in-water emulsion to adjust the pH value to 3. 0.12 parts by weight of the prepared melamine resin prepolymer was slowly added dropwise to the oil-in-water emulsion. The mixture was stirred at 800 r / min and reacted at 90℃ for 1 h. After the reaction was completed, the resulting mixed solution was filtered, washed twice with water and ethanol respectively, and dried in an oven at 60℃ for 9 h to obtain the pre-coated material.
[0123] (3) Dissolve 0.17 parts by weight of chlorinated rubber in 5 parts by weight of dichloromethane, add 1 part by weight of the pre-coated material, and stir thoroughly. Add the resulting mixture to 20 parts by weight of water, stir at 800 r / min, and raise the temperature until the solvent evaporates, so that the chlorinated rubber gradually forms a film and adheres to the outer wall of the inner wall coating repair material to obtain organic microcapsules.
[0124] The elastic modulus of the organic microcapsules was measured to be 0.5 GPa using a nanoindenter. Scanning electron microscopy was used to measure the combined thickness of the capsule wall and membrane encapsulation material in frozen sections of the microcapsules, which was found to be 0.9 μm, consistent with the calculation formula Y = 0.42X. 2 -0.92X+T. Testing revealed that the mass ratio of the core, wall, and membrane encapsulation material in this organic microcapsule was 1:0.87:0.3. The size of the organic microcapsule was 3–6 μm.
[0125] (4) Add 1 part by weight of terpine acetate to 3 parts by weight of water at 80°C, add 0.2 parts by weight of octylphenol polyoxyethylene ether, shear emulsify at 4000 r / min for 20 min using a shear machine, adjust the pH value to 3, add 1.1 parts by weight of tetraethyl orthosilicate, react for 16 h, wash and filter according to routine, and dry at 90°C for 8 h to obtain silica microcapsules coated with active components.
[0126] (5) 1 part by weight of silica microcapsules coated with active components and 0.1 part by weight of γ-mercaptopropyltrimethoxysilane were added to 30 parts by weight of toluene. The surface modification reaction was carried out at 110°C under reflux for 3 hours. After cooling, the surface was filtered and washed with ethanol and dried at 90°C for 5 hours to obtain surface-modified silica microcapsules.
[0127] (6) One part by weight of surface-modified silica microcapsules was added to 10 parts by weight of a 30% hydrogen peroxide solution. After oxidation at 80°C for 1 hour, the microcapsules were washed twice with water and ethanol, respectively, and dried at 60°C for 10 hours to obtain inorganic microcapsules. The mass ratio of the capsule core to the capsule wall in the inorganic microcapsules was found to be 1:0.32. The size of the inorganic microcapsules was 1–4 μm.
[0128] (7) Add 0.2 parts by weight of organic microcapsules, 0.2 parts by weight of inorganic microcapsules and 0.1 parts by weight of 3-(3-methoxy-4-hydroxyphenyl)acrylic acid to 100 parts by weight of straight-run pitch (penetration of 70 1 / 10 mm at 25°C), and stir at 800 r / min for 3 h under heating conditions at 150°C to obtain purified pitch.
[0129] Comparative Example 1
[0130] The purified asphalt was prepared according to the method of Example 1, except that in step (1), the amount of water was increased to 15 parts by weight, and in step (3), the amount of chlorinated rubber was increased to 0.25 parts by weight. The resulting organic microcapsules were analyzed using a nanoindenter, and the elastic modulus of microcapsule D3 was found to be 3.0 GPa. Scanning electron microscopy was used to analyze frozen sections of the microcapsules, and the sum of the thickness of the capsule wall and the membrane encapsulation material was found to be 3.1 μm, which does not conform to the calculation formula Y = 0.42X. 2 -0.92X+T.
[0131] Comparative Example 2
[0132] The purified asphalt was prepared according to the method of Example 1, except that in step (7), no organic microcapsules were added, and the organic microcapsules were replaced with inorganic microcapsules of the same weight.
[0133] Comparative Example 3
[0134] The purified asphalt was prepared according to the method of Example 1, except that the antioxidant was not added in step (7).
[0135] Test case
[0136] Straight-run asphalt (70 1 / 10 mm penetration at 25°C), natural asphalt (50 1 / 10 mm penetration at 25°C), and SBS modified asphalt (60 1 / 10 mm penetration at 25°C) were used as asphalt matrices. Asphalt fumes were tested on the asphalt compositions prepared in the above examples and comparative examples. Specifically, asphalt fumes were enriched by heating at 163°C for 6 hours, and gas chromatography and total hydrocarbon analyzer were used to test and analyze the asphalt fumes.
[0137] Table 1. Asphalt Fume Test Results
[0138]
[0139] It should be emphasized that the above-mentioned content is only a specific embodiment of the present invention and should not be construed as limiting the present invention to the above description in specific implementation. For those skilled in the art, any simple deductions and improvements made without departing from the spirit and principles of the present invention should be considered within the scope of protection of the present invention.
Claims
1. A purified asphalt, characterized in that, The raw material components are included in parts by weight: Asphalt: 100 parts; Organic microcapsules: 0.05–0.2 parts; Inorganic microcapsules: 0.05–0.2 parts; Antioxidant: 0.01–0.1 parts; The organic microcapsule includes a core, a wall, and a membrane encapsulation material, wherein the wall encapsulates the outer layer of the core, and the membrane encapsulation material encapsulates the outer layer of the wall; the core includes a first active component, the wall includes resin, and the membrane encapsulation material includes rubber material.
2. The purified asphalt according to claim 1, characterized in that, The elastic modulus of the organic microcapsule and the sum of the thicknesses of the capsule wall and the membrane encapsulation material satisfy the following formula: Y=0.42X 2 -0.92X+T; Wherein, Y is the elastic modulus of the organic microcapsule, in GPa; X is the sum of the thicknesses of the capsule wall and the membrane encapsulation material, in μm; and T is 1 ± 0.
1.
3. The purified asphalt according to claim 1, characterized in that, In the organic microcapsules, the sum of the thickness of the capsule wall and the membrane encapsulation material is 0.2–8 μm, preferably 0.5–5 μm; And / or, the mass ratio of the core, wall and membrane encapsulation material in the organic microcapsule is 1:(0.7-1):(0.2-0.3).
4. The purified asphalt according to claim 1, characterized in that, The organic microcapsules have a size of less than 50 micrometers, preferably less than 20 micrometers, and more preferably 3 to 15 μm; And / or, the size of the inorganic microcapsules is less than 50 micrometers, preferably less than 20 micrometers, and more preferably 1 to 15 μm.
5. The purified asphalt according to claim 1, characterized in that, In the organic microcapsule, the first active component is one or more of aldehyde compounds and ketone compounds; Preferably, the aldehyde compound is selected from one or more of the following: p-methylbenzaldehyde, decanal, o-carboxybenzaldehyde, p-isopropylbenzaldehyde, cinnamaldehyde, p-hydroxybenzaldehyde, p-methoxybenzaldehyde, 2-methyl-3-(3,4-methylene-dioxyphenyl)propanal, 3,4-methylenedioxybenzaldehyde, 3-(4-isopropylphenyl)-2-methylpropanal, ethyl vanillin, phenylacetaldehyde, anisaldehyde, nonadien-2,6-aldehyde, 2,6-dimethyl-2,6-octadienal, vanillin, citronellol, neraldehyde, hydroxymethylpentylcyclohexene acetal, p-diethylaminobenzaldehyde, and undecenal. Preferably, the ketone compound is selected from one or more of 6-methyl-3,5-heptadien-2-one, 2-undecanone, acetophenone, ionone, irisone, methyl ionone, damasone, and dihydrodamasone.
6. The purified asphalt according to claim 1, characterized in that, The capsule wall is made of melamine resin; And / or, the rubber material is at least one of chlorinated rubber, styrene-butadiene rubber, and chloroprene rubber.
7. The purified asphalt according to claim 1, characterized in that, The inorganic microcapsule includes a core and a wall, wherein the wall is wrapped around the core; the core includes a second active component, and the wall includes organosilane-modified silica. And / or, the mass ratio of the capsule core to the capsule wall in the inorganic microcapsule is 1:(0.3 to 0.5).
8. The purified asphalt according to claim 7, characterized in that, In the inorganic microcapsule, the second active component is one or more ester compounds; Preferably, the ester compound is selected from one or more of the following: methyl salicylate, methyl cinnamate, ethyl cinnamate, ethyl phenylacetate, methyl phenylacetate, geraniol phenylacetate, phenylethyl phenylacetate, isoamyl phenylacetate, benzyl salicylate, p-methyl benzyl acetate, benzyl acetate, isobutyl benzoate, isoamyl salicylate, benzyl cinnamate, phenylethyl cinnamate, linaloyl formate, linaloyl acetate, linaloyl isobutyrate, menthyl acetate, terpineol acetate, and borneol acetate. And / or, in the inorganic microcapsules, the organosilane is a sulfonylsilane obtained by oxidizing mercaptosilane; the mercaptosilane is one or more of γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane.
9. The purified asphalt according to claim 1, characterized in that, The antioxidant is a carboxyl-containing antioxidant, preferably one or more of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)acrylic acid, 3-(3,5-dimethyl-4-hydroxyphenyl)acrylic acid, 3-(3,5-dimethoxy-4-hydroxyphenyl)acrylic acid, and 3-(3-methoxy-4-hydroxyphenyl)acrylic acid; And / or, the asphalt is at least one of straight-run asphalt, polymer-modified asphalt and natural asphalt; preferably, the asphalt has a penetration of 30 to 210 1 / 10 mm at 25°C.
10. A method for preparing purified asphalt according to any one of claims 1-9, characterized in that, include: Organic microcapsules and inorganic microcapsules were prepared separately, and then mixed evenly with antioxidants and asphalt under heating conditions to obtain purified asphalt.
11. The method according to claim 10, characterized in that, include: (1) Mix the first active component, the first emulsifier and water to form an oil-in-water emulsion; (2) The water-in-oil emulsion is reacted with the resin prepolymer, and then filtered, washed and dried to obtain the pre-coated material; (3) In the presence of a volatile solvent, the rubber material is mixed with the pre-coated material obtained in step (2), and then the resulting mixture is mixed with water and heated until the volatile solvent evaporates to obtain organic microcapsules; (4) The second active component, the second emulsifier and water are mixed and reacted with the silicon source. Then, the mixture is washed, filtered and dried to obtain silica microcapsules coated with the active component. (5) The silica microcapsules coated with the active components, organosilane and organic solvent are mixed and surface modification reaction is carried out. Then, after cooling, filtration, washing and drying, surface-modified silica microcapsules are obtained. (6) After mixing the surface-modified silica microcapsules with hydrogen peroxide solution for oxidation reaction, the microcapsules are washed and dried to obtain inorganic microcapsules. (7) The organic microcapsules, inorganic microcapsules and antioxidants are added to the asphalt and mixed evenly under heating conditions to obtain purified asphalt.
12. The method according to claim 11, characterized in that, In step (1), the weight ratio of the first active component, the first emulsifier, and water is 1:(0.05~0.09):(6~9).
13. The method according to claim 11, characterized in that, In step (2), before the oil-in-water emulsion reacts with the resin prepolymer, the pH value of the oil-in-water emulsion is adjusted to below 5, preferably to 2-4; And / or, in step (2), the weight ratio of the oil-in-water emulsion to the resin prepolymer is 1: (0.08～0.15)。 14. The method according to claim 11, characterized in that, In step (2), the resin prepolymer is a melamine resin prepolymer, which is prepared by the following method: Preferably, melamine and formaldehyde solutions are mixed and dissolved in water, and the pH value is adjusted to 7.5-9.
5. Then, the mixture is placed in a constant temperature water bath at 60-90°C and reacted with stirring for 0.5-3.5 hours. Preferably, the formaldehyde solution has a mass concentration of 30% to 40%; Preferably, the weight ratio of melamine, formaldehyde solution, and water is 1:(2-3):(8-10).
15. The method according to claim 11, characterized in that, In step (3), the weight ratio of the rubber material to the pre-coated material obtained in step (2) is (0.1~0.2):1; And / or, in step (3), the weight ratio of the rubber material, volatile solvent, and water is 1:(10-20):(50-150); And / or, the volatile solvent is selected from one or more of carbon tetrachloride, dichloromethane, and trichloroethylene.
16. The method according to claim 11, characterized in that, In step (4), the weight ratio of the second active component, the second emulsifier, water, and silicon source is 1:(0.05-0.3):(3-7):(1-5), preferably 1:(0.1-0.2):(4-5):(1-1.5); And / or, in step (4), the reaction conditions are: reaction time of 10 to 18 hours and reaction temperature of 60 to 80 degrees Celsius.
17. The method according to claim 11, characterized in that, In step (5), the organic solvent is one or more of xylene, toluene, cyclohexanone, chlorobenzene and pyridine; And / or, in step (5), the surface modification reaction is carried out at a temperature of 100℃ to 120℃ for a time of 1 to 3 hours.
18. The method according to claim 11, characterized in that, In step (6), the weight ratio of the surface-modified silica microcapsules to the hydrogen peroxide solution is 1:(5-10); the mass fraction of the hydrogen peroxide solution is 10%-30%. And / or, in step (6), the oxidation reaction is carried out at a temperature of 50–90°C for 1–5 hours.
19. The method according to claim 11, characterized in that, In step (7), the heating temperature is 140–180°C; And / or, the mixing is performed by mechanical stirring; preferably, the stirring speed is 500-1000 r / min and the stirring time is 1-3 h.