CN115353326A - Reflective anti-vehicle-mark asphalt and preparation method thereof - Google Patents

Reflective anti-vehicle-mark asphalt and preparation method thereof Download PDF

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CN115353326A
CN115353326A CN202210893380.0A CN202210893380A CN115353326A CN 115353326 A CN115353326 A CN 115353326A CN 202210893380 A CN202210893380 A CN 202210893380A CN 115353326 A CN115353326 A CN 115353326A
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asphalt
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魏玉芝
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02Macromolecular compounds
    • C04B26/26Bituminous materials, e.g. tar, pitch
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38Fibrous materials; Whiskers
    • C04B14/386Carbon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02Treatment
    • C04B20/023Chemical treatment
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16Sulfur-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0075Uses not provided for elsewhere in C04B2111/00 for road construction
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/80Optical properties, e.g. transparency or reflexibility
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength

Abstract

The invention discloses a reflective anti-vehicle-mark asphalt and a preparation method thereof, and relates to the technical field of asphalt concrete. According to the invention, firstly, mercaptobutyric acid, sodium hydroxide, carbon disulfide, [5- (4-amino-2-chloro-phenyl) -2-furan ] methanol, polytetrahydrofuran diol, isophorone diisocyanate and 1, 3-bis (4-maleimide phenoxy) benzene are utilized to obtain a modified hot melt adhesive, and the photo-thermal reversible self-repairing effect is achieved; then utilizing carbon nano fiber, glycine, 2', 5-dichloro-2-hydroxy-4-methylbenzophenone, 3- (oxiranylmethoxy) benzoic acid and 2-chlorocyclopentanone to obtain modified carbon fiber; then negative pressure treatment is carried out to form a compact net structure, so that the car mark resistance and the light aging resistance of the asphalt are enhanced. The asphalt prepared by the invention has the effects of preventing car marks and resisting light aging.

Description

Reflective anti-vehicle-mark asphalt and preparation method thereof
Technical Field
The invention relates to the technical field of asphalt concrete, in particular to reflective anti-vehicle-mark asphalt and a preparation method thereof.
Background
At present, in order to improve the visibility of a road surface at night and enable a driver to drive safely, glass beads are often added into asphalt concrete, and the light reflection characteristic of the glass beads can improve the brightness of the road surface under the irradiation of street lamps, car lamps and even weak moonlight at night. Asphalt pavement occupies a considerable proportion of highways due to its excellent service performance. However, in recent years, due to the limitations of the performance of the raw materials of the asphalt pavement, the increase of traffic volume and heavy-load overloaded vehicles, ruts appear to deteriorate the flatness of the pavement and cause other diseases such as net cracks, pits, holes and the like, and if the damage cannot be controlled in time, the ruts will be spread and cracked under the action of the outer load, so that the service life of the pavement structure is influenced, and the structure of the whole pavement is damaged.
Photo-oxidative aging is the main cause of long-term aging of asphalt roads. Ultraviolet energy exceeds the energy of broken bonds, and weak chemical bonds in asphalt molecules are broken to generate chemical reaction, so that the molecular structure is changed, and the performance is reduced. A large amount of condensed ring compounds, SBS modifiers and the like in the asphalt have strong ultraviolet absorption capacity, and undergo photolysis reaction to cause aging, thus influencing the service performance and the service life of roads. In western regions such as Xinjiang and Tibet in China, the altitude is high, the air is thin, the ultraviolet absorption radiation is particularly strong, the ultraviolet aging phenomenon can cause the temperature crack resistance and fatigue failure resistance of the asphalt pavement to be reduced, the pavement is easy to generate diseases such as cracks, pits and the like, and the service life of the asphalt pavement is shortened.
Disclosure of Invention
The invention aims to provide a reflective anti-vehicle-mark asphalt and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the reflective car-mark-proof asphalt mainly comprises foamed asphalt, modified hot melt adhesive, modified carbon fiber, glass beads, aggregate, LOF65-00 anti-stripping agent and mineral powder.
Further, the modified hot melt adhesive is prepared by reacting mercaptobutyric acid, sodium hydroxide and carbon disulfide, 5- (4-amino-2-chloro-phenyl) -2-furan ] methanol, polytetrahydrofuran diol, isophorone diisocyanate and 1, 3-bis (4-maleimide phenoxy) benzene.
Further, the modified carbon fiber is prepared from carbon nanofibers, glycine, 2', 5-dichloro-2-hydroxy-4-methylbenzophenone, 3- (oxiranylmethoxy) benzoic acid and 2-chlorocyclopentanone.
Further, the preparation method of the reflective anti-vehicle-mark asphalt comprises the following preparation steps:
(1) Mixing isophorone diisocyanate and N, N-dimethyl imide according to a mass ratio of 1.2-1, stirring at 50-60 ℃ and 80-100 rpm for 15-30 min, then adding polytetrahydrofuran diol 1000 and dibutyltin dilaurate according to a mass ratio of 1;
(2) Mixing a carbon fiber base material, sodium carbonate, trifluoroethanol and 2', 5-dichloro-2-hydroxy-4-methylbenzophenone according to a mass ratio of 1.0-1; mixing a modified precursor, 3- (ethylene oxide methoxyl) benzoic acid and chloroform according to the mass ratio of 1.4;
(3) Reacting the primary material, sodium carbonate, trifluoroethanol and 2-chlorocyclopentanone for 3-7 h at the mass ratio of 1.8-1.4;
(4) Mixing foamed asphalt, a modified hot melt adhesive and modified carbon fibers according to a mass ratio of 1.5.
Further, the preparation method of the trithiocarbonate in the step (1) comprises the following steps: mixing a mixed solution of sodium hydroxide and acetone according to a mass ratio of 1-18-1.
Further, the acetone mixed solution is prepared by mixing acetone and tetrahydrofuran according to a mass ratio of 1.13; the mercaptobutyric acid solution is prepared by mixing mercaptobutyric acid, acetone and tetrahydrofuran according to a mass ratio of 1.7.
Further, the preparation method of the carbon fiber base material in the step (2) comprises the following steps:
A. soaking the carbon nano fiber in acetone with the mass 2-5 times that of the carbon nano fiber, performing ultrasonic treatment at 25-35 kHz for 26-39 min, then soaking in absolute ethyl alcohol with the mass 3-7 times that of the carbon nano fiber, performing ultrasonic treatment at the same frequency for 20-36 min, then placing in nitric acid with the mass fraction of 65% and the mass 3-5 times that of the carbon nano fiber, and performing water bath treatment at 80-90 ℃ for 120-144 min to obtain pretreated carbon nano fiber;
B. placing the pretreated carbon nanofiber in a glycine solution with the mass 31-42 times that of the pretreated carbon nanofiber, wherein the mass ratio of glycine to deionized water in the glycine solution is 1.
Further, the length of the carbon nanofiber in the step A is 10-20 mu m, and the diameter of the carbon nanofiber is 150-200 nm.
Further, the preparation method of the foamed asphalt in the step (4) comprises the following steps: mixing the matrix asphalt at the temperature of 150-170 ℃ with the deionized water at the temperature of 40-50 ℃ according to the mass ratio of 100.
Further, the aggregate in the step (4) is one or a mixture of basalt, diabase, limestone or steel slag, and the particle size is 4.8-9.5 mm; the grain size of the glass beads is 2.4-4.7 mm.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes the foamed asphalt as the raw material, mixes with the modified hot melt adhesive and the modified carbon fiber, and realizes the effects of car mark prevention and ultraviolet aging resistance through negative pressure treatment.
Firstly, mercaptobutyric acid, sodium hydroxide and carbon disulfide react to form a trithio compound, and chloride ions of [5- (4-amino-2-chloro-phenyl) -2-furan ] methanol substitute sodium ions of the trithio compound to obtain trithiocarbonate, which can be repeatedly self-repaired under ultraviolet light, so that the car mark trace is repaired, and the asphalt has the car mark prevention effect; then polymerizing hydroxyl of polytetrahydrofuran diol and isocyanate group of isophorone diisocyanate to obtain polyurethane, and further reacting the isocyanate group with amino of trithiocarbonate; then the furyl reacts with maleimide of 1, 3-bis (4-maleimide phenoxy) benzene to form a thermally reversible covalent bond, and the thermally reversible self-repairing effect is achieved, so that the modified hot melt adhesive is obtained; then, negative pressure treatment is carried out, so that the modified hot melt adhesive and the modified carbon fibers are filled into holes and cracks of the foamed asphalt and are mutually crosslinked to form a compact network structure, the stress is mutually dispersed, the bearing capacity of the asphalt is increased, and the anti-vehicle mark property of the asphalt is enhanced; in addition, the modified carbon fiber has a photo-thermal conversion effect and has a synergistic effect with the modified hot melt adhesive, so that the self-repairing performance of the hot melt adhesive is improved, and the car mark prevention effect of the asphalt is enhanced.
Secondly, preparing modified carbon fibers from carbon nanofibers, glycine, 2', 5-dichloro-2-hydroxy-4-methylbenzophenone, 3- (oxiranylmethoxy) benzoic acid and 2-chlorocyclopentanone; the amino group of glycine is grafted on the surface of the carbon nanofiber, chloride ions of 2', 5-dichloro-2-hydroxy-4-methylbenzophenone react with carboxyl of the glycine, then hydroxyl of the glycine reacts with 3- (oxiranylmethoxy) benzoic acid to form a ring-opening reaction, and then the carboxyl of the 3- (oxiranylmethoxy) benzoic acid reacts with chloride ions of 2-chlorocyclopentanone to form a benzoate compound which acts together with a benzophenone group to effectively absorb ultraviolet rays and improve the ultraviolet aging resistance of the asphalt; in addition, the residual chloride ions on the surface of the modified carbon fibers can react with the hydroxyl groups of the modified hot melt adhesive, so that the modified carbon fibers are mutually crosslinked and stacked to form an ultraviolet absorption network, and the ultraviolet aging resistant effect of the asphalt is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method for testing each index of the reflective anti-vehicle-mark asphalt prepared in the following examples as follows:
pouring the asphalt of the same mass example and the asphalt of the same mass comparative example at 135 ℃, compacting by using a roller to prepare a test sample, and then carrying out car mark resistance and ultraviolet aging resistance effect tests;
anti-vehicle-mark property: testing stability and self-repairing effect;
stability: determining Marshall stability and dynamic stability with reference to JTG E20;
self-repairing: and cutting a section of the middle part of the test sample by using a blade to generate damage, wherein the undamaged depth is the thickness of two 1-yuan coins at the lower part of the sample, so that the damaged sample is subjected to self-repairing, and after the self-repairing is finished, the ductility is tested according to T0605, and the healing rate = repaired ductility/undamaged ductility.
Ultraviolet aging resistance: using 1200 μ w/cm 2 Irradiating for 8 days by an ultraviolet lamp, and carrying out three points on the asphalt before and after aging by referring to JTG E20And (4) bending test.
Example 1
(1) Mixing sodium hydroxide and acetone mixed liquor according to a mass ratio of 1.13, adding a mercaptobutyric acid solution with a mass of 194 times that of sodium hydroxide at 60rpm, wherein the mass ratio of mercaptobutyric acid to acetone to tetrahydrofuran in the acetone mixed liquor is 1;
(2) Mixing isophorone diisocyanate and N, N-dimethyl imide according to a mass ratio of 1.2, stirring at 50 ℃ and 80rpm for 15min, then adding polytetrahydrofuran diol 1000 and dibutyltin dilaurate according to a mass ratio of 1.00005, wherein the mass ratio of the polytetrahydrofuran diol 1000 to the isophorone diisocyanate is 1.5;
(3) Soaking carbon nanofibers with the length of 10 mu m and the diameter of 150nm in acetone with the mass of 2 times that of the carbon nanofibers, carrying out ultrasonic treatment at 25kHz for 26min, then soaking in absolute ethyl alcohol with the mass of 3 times that of the carbon nanofibers, carrying out ultrasonic treatment at the same frequency for 20min, then placing in nitric acid with the mass fraction of 65% and the mass of 3 times that of the carbon nanofibers, and carrying out water bath treatment at 80 ℃ for 120min to obtain pretreated carbon nanofibers;
(4) Placing the pretreated carbon nanofiber in a glycine solution with the mass ratio of glycine to deionized water being 1;
(5) Mixing a carbon fiber base material, sodium carbonate, trifluoroethanol and 2', 5-dichloro-2-hydroxy-4-methylbenzophenone according to a mass ratio of 1; mixing the modified precursor, 3- (ethylene oxide methoxyl) benzoic acid and chloroform according to the mass ratio of 1.4;
(6) Reacting the primary material, sodium carbonate, trifluoroethanol and 2-chlorocyclopentanone for 3h at the temperature of 55 ℃ and the frequency of 30kHz according to the mass ratio of 1.0;
(7) Mixing the matrix asphalt at 150 ℃ with the deionized water at 40 ℃ according to a mass ratio of 100; mixing foamed asphalt, a modified hot melt adhesive and modified carbon fibers according to a mass ratio of 1.5.
Example 2
(1) Mixing sodium hydroxide and acetone mixed liquor according to a mass ratio of 1.13, adding a mercaptobutyric acid solution with 21.5 times of the mass of sodium hydroxide at 70rpm, wherein the mass ratio of mercaptobutyric acid, acetone and tetrahydrofuran in the mercaptobutyric acid solution is 1;
(2) Mixing isophorone diisocyanate and N, N-dimethyl imide according to a mass ratio of 1.3, stirring at 55 ℃ and 90rpm for 23min, then adding polytetrahydrofuran diol 1000 and dibutyltin dilaurate according to a mass ratio of 1.00006, wherein the mass ratio of the polytetrahydrofuran diol 1000 to the isophorone diisocyanate is 1.75;
(3) Soaking carbon nanofibers with the length of 15 micrometers and the diameter of 175nm in acetone with the mass of 3.5 times that of the carbon nanofibers, carrying out ultrasonic treatment at 30kHz for 32min, then soaking in absolute ethyl alcohol with the mass of 5 times that of the carbon nanofibers, carrying out ultrasonic treatment at the same frequency for 28min, then placing in nitric acid with the mass fraction of 65% and the mass of 4 times that of the carbon nanofibers, and carrying out water bath treatment at 85 ℃ for 132min to obtain pretreated carbon nanofibers;
(4) Placing the pretreated carbon nanofiber in a glycine solution with the mass 36.5 times that of the pretreated carbon nanofiber, wherein the mass ratio of glycine to deionized water in the glycine solution is 1;
(5) Mixing a carbon fiber base material, sodium carbonate, trifluoroethanol and 2', 5-dichloro-2-hydroxy-4-methylbenzophenone according to a mass ratio of 1.1; mixing the modified precursor, 3- (oxiranylmethoxy) benzoic acid and chloroform according to a mass ratio of 1.55;
(6) Reacting the primary material, sodium carbonate, trifluoroethanol and 2-chlorocyclopentanone at the mass ratio of 1.2;
(7) Mixing the base asphalt at 160 ℃ with deionized water at 45 ℃ according to a mass ratio of 100; mixing foamed asphalt, a modified hot melt adhesive and modified carbon fibers according to a mass ratio of 1.65.
Example 3
(1) Mixing sodium hydroxide and acetone mixed liquor according to a mass ratio of 1.13, adding a mercaptobutyric acid solution with the mass of 24 times that of sodium hydroxide at 80rpm, wherein the mass ratio of mercaptobutyric acid to acetone to tetrahydrofuran in the mercaptobutyric acid solution is 1;
(2) Mixing isophorone diisocyanate and N, N-dimethyl imide according to a mass ratio of 1.4, stirring at 60 ℃ and 100rpm for 30min, then adding polytetrahydrofuran diol 1000 and dibutyltin dilaurate according to a mass ratio of 1:0.00007, wherein the mass ratio of the polytetrahydrofuran diol 1000 to the isophorone diisocyanate is 2;
(3) Soaking carbon nanofibers with the length of 20 mu m and the diameter of 200nm in acetone with the mass 5 times that of the carbon nanofibers, carrying out 35kHz ultrasonic treatment for 39min, then soaking in absolute ethyl alcohol with the mass 7 times that of the carbon nanofibers, carrying out ultrasonic treatment for 36min at the same frequency, then placing in nitric acid with the mass fraction 65% and the mass 5 times that of the carbon nanofibers, and carrying out 90-DEG C water bath treatment for 144min to obtain pretreated carbon nanofibers;
(4) Placing the pretreated carbon nanofiber in a glycine solution with the mass ratio of glycine to deionized water being 1;
(5) Mixing a carbon fiber base material, sodium carbonate, trifluoroethanol and 2', 5-dichloro-2-hydroxy-4-methylbenzophenone according to a mass ratio of 1.4; mixing the modified precursor, 3- (ethylene oxide methoxyl) benzoic acid and chloroform according to the mass ratio of 1.7;
(6) Reacting the primary material, sodium carbonate, trifluoroethanol and 2-chlorocyclopentanone at the mass ratio of 1.4;
(7) Mixing matrix asphalt at 170 ℃ with deionized water at 50 ℃ according to a mass ratio of 100; mixing foamed asphalt, modified hot melt adhesive and modified carbon fiber according to the mass ratio of 1.8.
Comparative example 1
Comparative example 1 differs from example 2 in that there is no step (1) and step (2) is changed to: mixing isophorone diisocyanate and N, N-dimethyl imide according to a mass ratio of 1.3, stirring at 55 ℃ and 90rpm for 23min, adding polytetrahydrofuran diol 1000 and dibutyltin dilaurate according to a mass ratio of 1:0.00006, wherein the mass ratio of the polytetrahydrofuran diol 1000 to the isophorone diisocyanate is 1.75. The rest of the preparation steps are the same as example 2.
Comparative example 2
Comparative example 2 differs from example 2 in that step (2) is different, step (2) being changed to: mixing isophorone diisocyanate and N, N-dimethyl imide according to a mass ratio of 1.3, stirring at 55 ℃ and 90rpm for 23min, then adding polytetrahydrofuran diol 1000 and dibutyltin dilaurate according to a mass ratio of 1.00006, wherein the mass ratio of the polytetrahydrofuran diol 1000 to the isophorone diisocyanate is 1.75. The rest of the preparation steps are the same as example 2.
Comparative example 3
Comparative example 3 differs from example 2 in that step (7) is different, step (7) being changed to: mixing the base asphalt at 160 ℃ with deionized water at 45 ℃ according to a mass ratio of 100; mixing foamed asphalt, modified hot melt adhesive and modified carbon fiber according to the mass ratio of 1.65 to 0.14, stirring at 70 ℃ and 350rpm for 45min, adding limestone with the particle size of 7.2mm, which is 2.7 times of the mass of the foamed asphalt, continuously stirring at 125 ℃ for 15s, then adding LOF65-00 antistripping agent with the particle size of 0.002 time of the mass of the foamed asphalt, glass beads with the particle size of 3.6mm, which is 0.12 times of the mass of the foamed asphalt, continuously stirring at 147 ℃ for 33s, then adding mineral powder with the mass of 0.9 time of the foamed asphalt, deionized water with the mass of 0.23 time of the foamed asphalt, and continuously stirring at 115 ℃ for 45s to obtain the reflective anti-vehicle mark asphalt. The rest of the preparation steps are the same as example 2.
Comparative example 4
Comparative example 4 differs from example 2 in that step (5) is different, step (5) being changed to: mixing a carbon fiber base material, 3- (ethylene oxide methoxyl) benzoic acid and chloroform according to the mass ratio of 1.55. The rest of the preparation steps are the same as example 2.
Comparative example 5
Comparative example 5 differs from example 2 in that step (6) is not present and step (5) is changed to: mixing a carbon fiber base material, sodium carbonate, trifluoroethanol and 2', 5-dichloro-2-hydroxy-4-methylbenzophenone according to a mass ratio of 1.1; mixing the modified precursor, 3- (ethylene oxide methoxyl) benzoic acid and chloroform according to the mass ratio of 1.55. The rest of the preparation steps are the same as example 2.
Examples of effects
Table 1 below shows the results of performance analysis of the reflective anti-vehicle-marking asphalt using examples 1 to 3 of the present invention and comparative examples 1 to 5.
TABLE 1
Figure BDA0003768446060000091
Figure BDA0003768446060000101
The comparison of the stability and the healing rate data of the embodiment and the comparative example shows that trithiocarbonate obtained by the invention by utilizing mercaptobutyric acid, sodium hydroxide, carbon disulfide and [5- (4-amino-2-chloro-phenyl) -2-furan ] methanol can be repeatedly self-repaired under ultraviolet light, so that the car mark trace can be repaired, and the asphalt has the car mark prevention effect; then, the modified hot melt adhesive is obtained by using polytetrahydrofuran diol, isophorone diisocyanate, trithiocarbonate and maleimide of 1, 3-bis (4-maleimide phenoxy) benzene, contains a thermally reversible covalent bond and has a thermally reversible self-repairing effect; through negative pressure treatment, the foamed asphalt is filled, the modified hot melt adhesive and the modified carbon fiber are mutually crosslinked to form a compact network structure, and the anti-vehicle-mark property of the asphalt is enhanced; from comparison of the data before and after aging of examples and comparative examples, it can be seen that the present invention produces modified carbon fibers using carbon nanofibers, glycine, 2', 5-dichloro-2-hydroxy-4-methylbenzophenone, 3- (oxiranylmethoxy) benzoic acid, 2-chlorocyclopentanone; the benzoate group and the benzophenone group act together to effectively absorb ultraviolet rays and improve the ultraviolet aging resistance of the asphalt; in addition, the modified carbon fibers can react with the modified hot melt adhesive, so that the modified carbon fibers are mutually crosslinked and stacked to form an ultraviolet absorption network, and the ultraviolet aging resistant effect of the asphalt is enhanced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1.一种反光防车印沥青,其特征在于,主要包括泡沫沥青、改性热熔胶、改性碳纤维、玻璃微珠、集料、LOF65-00抗剥落剂、矿粉。1. A reflective anti-car printing asphalt is characterized in that it mainly includes foamed asphalt, modified hot-melt adhesive, modified carbon fiber, glass microspheres, aggregate, LOF65-00 anti-stripping agent, mineral powder. 2.根据权利要求1所述的一种反光防车印沥青,其特征在于,所述改性热熔胶由巯基丁酸、氢氧化钠、二硫化碳反应、[5-(4-氨基-2-氯-苯基)-2-呋喃]甲醇、聚四氢呋喃二醇、异佛尔酮二异氰酸酯、1,3-双(4-马来酰亚胺苯氧基)苯制得。2. a kind of reflective anti-vehicle printing asphalt according to claim 1, is characterized in that, described modified hot-melt adhesive is reacted by mercaptobutyric acid, sodium hydroxide, carbon disulfide, [5-(4-amino-2- Chlorine - phenyl) -2-furan] methanol, polytetrahydrofuran diol, isophorone diisocyanate, 1,3-bis (4-maleimide phenoxy) benzene in the system. 3.根据权利要求1所述的一种反光防车印沥青,其特征在于,所述改性碳纤维由碳纳米纤维、甘氨酸、2',5-二氯-2-羟基-4-甲基二苯甲酮、3-(环氧乙烷基甲氧基)苯甲酸、2-氯环戊酮制得。3. A kind of reflective anti-vehicle printing asphalt according to claim 1, characterized in that, the modified carbon fiber is made of carbon nanofibers, glycine, 2', 5-dichloro-2-hydroxyl-4-methyl bismuth Benzophenone, 3-(oxiranyl methoxy) benzoic acid, 2-chlorocyclopentanone in the system. 4.一种反光防车印沥青的制备方法,其特征在于,包括以下制备步骤:4. A preparation method for reflective anti-vehicle asphalt, characterized in that it comprises the following preparation steps: (1)将异佛尔酮二异氰酸酯、N,N-二甲基酰亚胺按质量比1:0.2~1:0.4混合,50~60℃、80~100rpm搅拌15~30min后,再按质量比1:0.00005~1:0.00007加入聚四氢呋喃二醇1000、二月桂酸二丁基锡,聚四氢呋喃二醇1000与异佛尔酮二异氰酸酯的质量比为1.5:1~2.0:1,升温至75~83℃,反应2~5h后,降温至34~42℃,加入异佛尔酮二异氰酸酯质量0.3~0.5倍的三硫代碳酸酯,反应58~73min后,升温至57~68℃,反应3~6h后,加入异佛尔酮二异氰酸酯质量0.5~0.8倍的1,3-双(4-马来酰亚胺苯氧基)苯,升温至77~83℃,反应4~7h,得改性热熔胶;(1) Mix isophorone diisocyanate and N,N-dimethylimide at a mass ratio of 1:0.2 to 1:0.4, stir at 50 to 60°C and 80 to 100 rpm for 15 to 30 minutes, and then Ratio 1:0.00005~1:0.00007 Add polytetrahydrofuran diol 1000 and dibutyltin dilaurate, the mass ratio of polytetrahydrofuran diol 1000 to isophorone diisocyanate is 1.5:1~2.0:1, heat up to 75~83 ℃, after 2-5 hours of reaction, lower the temperature to 34-42 ℃, add trithiocarbonate which is 0.3-0.5 times the mass of isophorone diisocyanate, react for 58-73 minutes, raise the temperature to 57-68 ℃, and react for 3- After 6 hours, add 1,3-bis(4-maleimidephenoxy)benzene, which is 0.5-0.8 times the mass of isophorone diisocyanate, raise the temperature to 77-83°C, and react for 4-7 hours to obtain the modified hot melt adhesive; (2)将碳纤维基料、碳酸钠、三氟乙醇、2',5-二氯-2-羟基-4-甲基二苯甲酮按质量比1:0.9:9:3.0~1:1.4:13:5.2混合,52~64℃、25~35kHz下反应2~6h后,取出,用乙酸乙酯洗涤5~7次,得改性前体;将改性前体、3-(环氧乙烷基甲氧基)苯甲酸、氯仿按质量比1:0.4:4~1:0.7:7混合,搅拌均匀后,加入改性前体质量0.2~0.4倍的Amberlyst-15,55~67℃、30~40kHz下反应3~7h后,取出,用无水乙醇洗涤6~8次,得初料;(2) Carbon fiber base material, sodium carbonate, trifluoroethanol, 2', 5-dichloro-2-hydroxy-4-methylbenzophenone in mass ratio 1:0.9:9:3.0~1:1.4: 13:5.2 mixed, reacted at 52~64°C, 25~35kHz for 2~6h, took it out, washed 5~7 times with ethyl acetate to obtain a modified precursor; the modified precursor, 3-(ethylene oxide Alkylmethoxy)benzoic acid and chloroform are mixed according to the mass ratio of 1:0.4:4~1:0.7:7. After stirring evenly, add Amberlyst-15 which is 0.2~0.4 times the mass of the modified precursor, 55~67℃, After reacting at 30-40kHz for 3-7 hours, take it out, wash it with absolute ethanol for 6-8 times, and get the initial material; (3)将初料、碳酸钠、三氟乙醇、2-氯环戊酮按质量比1:1.0:11:2.8~1:1.4:17:5.2,55~70℃、30~40kHz下反应3~7h后,取出,用乙酸乙酯洗涤5~7次,得改性碳纤维;(3) The initial material, sodium carbonate, trifluoroethanol, and 2-chlorocyclopentanone are reacted at 55-70°C and 30-40kHz in a mass ratio of 1:1.0:11:2.8~1:1.4:17:5.2. After ~7h, take it out and wash it with ethyl acetate for 5~7 times to obtain modified carbon fiber; (4)将泡沫沥青、改性热熔胶、改性碳纤维按质量比1:0.5:0.08~1:0.8:0.2混合,60~80℃、300~400rpm搅拌38~52min后,于0.02~0.08MPa处理2~10min后,加入泡沫沥青质量2.0~3.5倍的集料,110~140℃下继续搅拌10~20s,然后加入泡沫沥青质量0.001~0.003倍的LOF65-00抗剥落剂、泡沫沥青质量0.04~0.2倍的玻璃微珠,126~168℃下继续搅拌26~40s,然后加入泡沫沥青质量0.4~1.4倍的矿粉、泡沫沥青质量0.15~0.30倍的去离子水,100~130℃继续搅拌30~60s,得反光防车印沥青。(4) Mix foamed asphalt, modified hot melt adhesive, and modified carbon fiber at a mass ratio of 1:0.5:0.08 to 1:0.8:0.2, stir at 60 to 80°C and 300 to 400 rpm for 38 to 52 minutes, and then mix at 0.02 to 0.08 After MPa treatment for 2-10 minutes, add aggregates 2.0-3.5 times the mass of foamed asphalt, continue stirring at 110-140°C for 10-20s, then add 0.001-0.003 times the mass of foamed asphalt LOF65-00 anti-stripping agent and foamed asphalt 0.04-0.2 times the glass beads, continue stirring at 126-168°C for 26-40s, then add mineral powder 0.4-1.4 times the mass of foamed asphalt, deionized water 0.15-0.30 times the mass of foamed asphalt, continue at 100-130°C Stir for 30-60 seconds to obtain reflective and anti-car print asphalt. 5.根据权利要求4所述的一种反光防车印沥青的制备方法,其特征在于,步骤(1)所述三硫代碳酸酯的制备方法为:将氢氧化钠、丙酮混合液按质量比1:18~1:22混合,60~80rpm下加入氢氧化钠质量19~24倍的巯基丁酸溶液,反应8~16min后,加入氢氧化钠质量8~11倍的二硫化碳溶液,二硫化碳溶液中二硫化碳和丙酮的质量比为1:0.63,反应9~19min后,加入氢氧化钠质量2~4倍的[5-(4-氨基-2-氯-苯基)-2-呋喃]甲醇,反应27~39min后,200~300rpm、64~73℃蒸馏5~8h后,加入氢氧化钠质量7~12倍的二氯甲烷,依次用质量分数为10%的盐酸、去离子水、饱和食盐水洗涤4~6次,200~300rpm、38~44℃蒸馏3~6h后,于40~50℃干燥6~9h。5. the preparation method of a kind of reflective anti-vehicle printing asphalt according to claim 4 is characterized in that, the preparation method of trithiocarbonate described in step (1) is: sodium hydroxide, acetone mixed solution Mix at a ratio of 1:18 to 1:22, add mercaptobutyric acid solution with 19 to 24 times the mass of sodium hydroxide at 60 to 80 rpm, react for 8 to 16 minutes, add carbon disulfide solution with 8 to 11 times the mass of sodium hydroxide, carbon disulfide solution The mass ratio of carbon disulfide and acetone is 1:0.63. After reacting for 9 to 19 minutes, add [5-(4-amino-2-chloro-phenyl)-2-furan]methanol with 2 to 4 times the mass of sodium hydroxide, After reacting for 27 to 39 minutes, distill at 200 to 300 rpm at 64 to 73°C for 5 to 8 hours, add dichloromethane that is 7 to 12 times the mass of sodium hydroxide, and use 10% hydrochloric acid, deionized water, and saturated salt in sequence Wash with water for 4 to 6 times, distill at 200 to 300 rpm and 38 to 44°C for 3 to 6 hours, and then dry at 40 to 50°C for 6 to 9 hours. 6.根据权利要求5所述的一种反光防车印沥青的制备方法,其特征在于,所述丙酮混合液为丙酮和四氢呋喃按质量比1:1.13混合;所述巯基丁酸溶液为巯基丁酸、丙酮、四氢呋喃按质量比1:3.7:4.2混合。6. the preparation method of a kind of reflective anti-car printing asphalt according to claim 5, is characterized in that, described acetone mixed solution is acetone and THF mix by mass ratio 1:1.13; Described mercaptobutyric acid solution is mercaptobutyl Acid, acetone, and tetrahydrofuran were mixed in a mass ratio of 1:3.7:4.2. 7.根据权利要求4所述的一种反光防车印沥青的制备方法,其特征在于,步骤(2)所碳纤维基料的制备方法为:7. the preparation method of a kind of reflective anti-vehicle printing asphalt according to claim 4, is characterized in that, the preparation method of step (2) institute carbon fiber base material is: A、碳纳米纤维浸泡于碳纳米纤维质量2~5倍的丙酮,25~35kHz超声26~39min后,再浸泡于碳纳米纤维质量3~7倍的无水乙醇,相同频率下超声20~36min,然后置于碳纳米纤维质量3~5倍的质量分数为65%的硝酸,80~90℃水浴处理120~144min,得预处理碳纳米纤维;A. Carbon nanofibers are soaked in acetone with 2-5 times the mass of carbon nanofibers, ultrasonicated at 25-35kHz for 26-39 minutes, then soaked in absolute ethanol with 3-7 times the mass of carbon nanofibers, ultrasonicated at the same frequency for 20-36 minutes , and then placed in nitric acid with a mass fraction of 3 to 5 times the mass of the carbon nanofibers being 65%, and treated in a water bath at 80 to 90° C. for 120 to 144 minutes to obtain pretreated carbon nanofibers; B、将预处理碳纳米纤维置于预处理碳纳米纤维质量31~42倍的甘氨酸溶液,甘氨酸溶液中甘氨酸和去离子水的质量比为1:100,升温至150~162℃,反应170~210min后,降至室温,取出,用去离子水冲洗6~10min,于50~60℃烘干5~9h。B. Place the pretreated carbon nanofibers in a glycine solution that is 31 to 42 times the mass of the pretreated carbon nanofibers. The mass ratio of glycine and deionized water in the glycine solution is 1:100, and the temperature is raised to 150~162°C, and the reaction is 170~ After 210 minutes, cool down to room temperature, take it out, rinse with deionized water for 6-10 minutes, and dry at 50-60°C for 5-9 hours. 8.根据权利要求7所述的一种反光防车印沥青的制备方法,其特征在于,所述步骤A碳纳米纤维长度为10~20μm,直径为150~200nm。8 . The method for preparing reflective anti-vehicle asphalt according to claim 7 , wherein the carbon nanofibers in step A have a length of 10-20 μm and a diameter of 150-200 nm. 9.根据权利要求4所述的一种反光防车印沥青的制备方法,其特征在于,步骤(4)所述泡沫沥青的制备方法为:将150~170℃的基质沥青与40~50℃的去离子水按质量比100:3混合,90~110bar下发泡20~60s。9. The preparation method of a kind of reflective anti-car printing asphalt according to claim 4, characterized in that, the preparation method of the foamed asphalt described in step (4) is: mixing base asphalt at 150-170°C with 40-50°C The deionized water is mixed according to the mass ratio of 100:3, and foamed at 90-110bar for 20-60s. 10.根据权利要求4所述的一种反光防车印沥青的制备方法,其特征在于,步骤(4)所述集料为玄武岩、辉绿岩、石灰岩或钢渣的一种或多种混合,粒径为4.8~9.5mm;所述玻璃微珠的粒径为2.4~4.7mm。10. the preparation method of a kind of reflective anti-vehicle asphalt according to claim 4, is characterized in that, the aggregate described in step (4) is one or more mixes of basalt, diabase, limestone or steel slag, The particle diameter is 4.8-9.5mm; the particle diameter of the glass microspheres is 2.4-4.7mm.
CN202210893380.0A 2022-07-27 2022-07-27 Reflective anti-vehicle-mark asphalt and preparation method thereof Pending CN115353326A (en)

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Application publication date: 20221118