Road marking functional coating for long-acting light reflection and preparation method thereof

Abstract

The invention relates to the technical field of long-acting reflective road marking coatings, and discloses a long-acting reflective road marking functional coating and a preparation method thereof. Comprising the following raw materials: 40-60 parts of polyacrylic resin emulsion, 1-3 parts of a defoaming agent, 3-5 parts of modified nano silicon carbide, 1-3 parts of modified glass beads, 4-10 parts of filler, 1-3 parts of a curing agent, 2-5 parts of a dispersing agent and 30-35 parts of deionized water. Nano silicon carbide is modified by maleic anhydride and then grafted with polyphenyl ether, the interfacial compatibility of the nano silicon carbide and a matrix is improved by the polyphenyl ether, uniform dispersion of the nano silicon carbide is promoted, agglomeration is inhibited, and the wear resistance and impact resistance of the coating are greatly improved; high-density directional distribution of ultraviolet absorbing groups is achieved, the transparency of the coating is kept, a surface grafting layer inhibits a photooxidation chain reaction, and the anti-aging capacity of the coating is greatly improved.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and particularly relates to a road marking functional coating for long-term reflection and its preparation method. Background Art

[0002] With the rapid development of transportation infrastructure, road markings, as a core element of traffic safety, have an increasing demand for durability and functionality. Traditional reflective road marking coatings mostly rely on glass microspheres to achieve optical reflection, but in long-term use, the reflective performance is prone to decay due to mechanical wear and aging, affecting night driving safety. In the prior art, the problems of insufficient abrasion resistance and anti-aging properties of coatings are particularly prominent, and there is an urgent need to develop functional coatings with both long-term reflection and high durability.

[0003] Currently, the abrasion resistance of commercially available marking coatings mainly depends on the mechanical strength of the resin base material and the reinforcement effect of fillers. For example, although acrylic resin-based coatings have certain toughness, they are prone to scratches or peeling under long-term vehicle rolling and sandstone friction, resulting in a decrease in the surface roughness of the markings and the shedding of reflective particles. Research shows that optimizing the dosage of fillers can improve the hardness of the coating, but excessive addition may cause interfacial stress concentration and accelerate wear instead. In addition, traditional film-forming aids have limited effect on improving abrasion resistance and may reduce the adhesion of the coating. In the prior art, it is found through orthogonal experiments that the dosage of luminous powder has a significant impact on abrasion resistance, but the compatibility problem with the resin matrix has not been completely solved, resulting in a non-linear change in the wear value over time and making it difficult to meet the long-term requirements.

[0004] The anti-aging property of marking coatings is mainly affected by ultraviolet rays, humidity and heat, and chemical erosion. In conventional reflective road marking coatings, generally, ultraviolet absorbers are added to improve the anti-ultraviolet effect of the coatings. Although it can partially alleviate photodegradation, small molecule ultraviolet absorbers are prone to precipitation, resulting in an insufficiently persistent anti-ultraviolet effect. Based on this, the present invention provides a road marking functional coating for long-term reflection and its preparation method, which can solve the problems existing in the prior art. Summary of the Invention

[0005] In order to solve the problems mentioned in the background art, the purpose of the present invention is to provide a road marking functional coating for long-term reflection and its preparation method.

[0006] The purpose of the present invention can be achieved by the following technical solutions: A road marking functional coating for long-term reflection, by weight, comprises the following raw materials: 40 - 60 parts of polyacrylic resin emulsion, 1 - 3 parts of defoamer, 3 - 5 parts of modified nano silicon carbide, 1 - 3 parts of modified glass microspheres, 4 - 10 parts of filler, 1 - 3 parts of curing agent, 2 - 5 parts of dispersant, and 30 - 35 parts of deionized water.

[0007] Further, the defoaming agent is tributyl phosphate or fatty alcohol polyoxyethylene ether.

[0008] Further, the filler is any one of quartz powder, heavy calcium carbonate, and magnesium hydroxide.

[0009] Further, the dispersant is sodium polyacrylate or ammonium polyacrylate.

[0010] Further, the preparation method of the modified nano-silicon carbide comprises the following steps: Step A1: Immerse the nano-silicon carbide powder in concentrated sulfuric acid, stir at 80 - 100 °C for 3 - 5 h, perform centrifugal separation and then wash until neutral to obtain the nano-silicon carbide intermediate, and vacuum dry for standby; Step A2: Disperse the nano-silicon carbide intermediate in toluene, then add maleic anhydride and a catalyst, react at 80 - 100 °C in an oil bath environment for 4 - 6 h, then perform centrifugal separation to obtain the solid material, wash and dry to obtain the intermediate product. Step A3: Disperse the intermediate product in N,N-dimethylformamide, ultrasonicate for 30 - 50 min, then add 4-dimethylaminopyridine and N,N'-dicyclohexylcarbodiimide, stir at 40 - 50 °C for 2 - 4 h, continue to add polyphenylene ether, after adding, raise the temperature to 120 - 130 °C, magnetically stir for 12 - 16 h, separate the product, wash and vacuum dry to obtain the modified nano-silicon carbide.

[0011] In the above technical solution, the nano-silicon carbide is acid-treated to make its surface rich in hydroxyl groups. The hydroxyl groups on the surface of the nano-silicon carbide react with the anhydride groups of maleic anhydride to form nano-silicon carbide with carboxylic acid on the surface. The hydroxyl groups contained in the polyphenylene ether react with the carboxylic acid groups, thereby grafting the polyphenylene ether onto the modified nano-silicon carbide through chemical bonds.

[0012] Further, in Step A2, the mass ratio of the nano-silicon carbide intermediate to maleic anhydride is 8:1 - 2.

[0013] Further, in Step A2, the catalyst is p-toluenesulfonic acid or methanesulfonic acid.

[0014] Further, the preparation method of the modified glass microspheres comprises the following steps: Step B1: Immerse the glass microspheres in concentrated sulfuric acid, soak for 2 - 5 h, then perform cleaning, and then vacuum dry to obtain the glass microsphere intermediate; Step B2: Ultrasonically disperse the glass microsphere intermediate in toluene, add the silane coupling agent KH-560, ultrasonicate for 15 - 20 min, then continuously stir at 60 - 80 °C in an oil bath condition for 3 - 5 h. After the reaction is completed, perform centrifugal separation, washing, and vacuum drying to obtain the modified glass microsphere intermediate; Step B3: Ultrasonically disperse the modified glass bead intermediate in toluene solution, then add catalyst Amberlyst-15 and 2,4-dihydroxybenzophenone into the solution, heat to 60 - 80 °C, react for 3 h. After the reaction is completed, filter, wash, and dry under vacuum to obtain the modified glass beads.

[0015] In the above technical solution, the glass beads are treated with silane coupling agent to make the surface rich in epoxy groups. 2,4-dihydroxybenzophenone can react with the epoxy groups on the surface of the glass beads under the catalysis of the catalyst, graft 2,4-dihydroxybenzophenone onto the surface of the glass beads through chemical bonds, thereby obtaining the modified glass beads.

[0016] Further, in step B2, the volume fraction of the ethanol solution is 65 - 75%.

[0017] A preparation method of a road marking functional coating for long-term retroreflection includes the following steps: Step 1: Mix the polyacrylic resin emulsion and modified nano-silicon carbide evenly. After mixing, add filler, modified glass beads, dispersant, and deionized water into a mixer, stir evenly, then add defoamer and let it stand to form a premix. Step 2: Stir the premix and the curing agent evenly, and store at room temperature.

[0018] Advantages of the present invention: (1) In the present invention, nano-silicon carbide with polyphenylene ether on its surface is prepared as a functional additive for the coating. The presence of polyphenylene ether forms a strong interfacial bond between the nano-silicon carbide and the film-forming substance matrix of the coating, promotes the uniform dispersion of the nano-silicon carbide, thereby optimizing the stress transfer efficiency and greatly improving the wear resistance and impact resistance of the coating.

[0019] (2) In the present invention, glass beads containing benzophenone structure are prepared to realize the uniform distribution of ultraviolet absorption groups, which can effectively absorb ultraviolet light. The glass beads, as a rigid carrier, can enhance the mechanical strength of the coating. After grafting, a core-shell structure is formed, which produces a synergistic effect between the ultraviolet absorber and the glass beads, not only maintaining the transparency of the coating, but also delaying the yellowing and powdering of the resin, and greatly improving the anti-aging ability of the glass beads.

[0020] Of course, it is not necessary for any product implementing the present invention to achieve all the above advantages simultaneously. Description of the Drawings

[0021] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for describing the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0022] Figure 1 It is the infrared test diagram of the nano-silicon carbide intermediate and the modified nano-silicon carbide in Example 1; Figure 2 It is the infrared test diagram of the glass microsphere intermediate and the modified glass microsphere in Example 1. Detailed implementation manners

[0023] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0024] Example 1, a road marking functional coating for long-term reflection, by weight, includes the following raw materials: 40 parts of polyacrylic resin emulsion, 3 parts of defoaming agent tributyl phosphate, 3 parts of modified nano-silicon carbide, 1 part of modified glass microspheres, 4 parts of filler heavy calcium carbonate, 1 part of curing agent aziridine, 3 parts of dispersant sodium polyacrylate, and 35 parts of deionized water.

[0025] The preparation method of the coating includes the following steps: Step 1: Mix the polyacrylic resin emulsion with the modified nano-silicon carbide. After mixing, add the filler heavy calcium carbonate, the modified glass microspheres, the dispersant sodium polyacrylate, and the deionized water into a mixer, stir evenly, and then add the defoaming agent tributyl phosphate and let it stand to form a premix; Step 2: Stir the premix with the curing agent aziridine evenly, and store it at room temperature.

[0026] Among them, the modified nano-silicon carbide is prepared by the following method: Step A1: Immerse 1.2 g of nano-silicon carbide powder in 20 ml of concentrated sulfuric acid, stir at 80 °C for 3 h, perform centrifugal separation, and wash until neutral to obtain a nano-silicon carbide intermediate, and vacuum dry it for later use; Step A2: Disperse 1.8 g of the nano-silicon carbide intermediate in 30 ml of toluene, then add 0.2 g of maleic anhydride and 0.05 g of catalyst p-toluenesulfonic acid, react at 80 °C in an oil bath environment for 4 h, then centrifugally separate the solid material, wash and dry to obtain an intermediate product; Step A3: Disperse 1.6 g of the intermediate product in 30 ml of N,N-dimethylformamide, ultrasonicate for 30 - 50 min, then add 0.16 g of 4-dimethylaminopyridine and 0.05 g of N,N'-dicyclohexylcarbodiimide, stir at 50 °C for 2 h, continue to add 1.2 g of polyphenylene ether. After addition, raise the temperature to 120 °C and magnetically stir for 12 h. Separate the product, wash it, and dry it under vacuum to obtain modified nano-silicon carbide.

[0027] The infrared test comparison schematic diagram of nano-silicon carbide and modified nano-silicon carbide is as Figure 1 shown. In the infrared test spectrum of nano-silicon carbide, the O-H characteristic absorption peak of nano-silicon carbide is at 3364 cm-1, and the Si-C characteristic absorption peak is at 889 cm-1. In the infrared test spectrum of modified nano-silicon carbide, the O-H characteristic absorption peak is at 3189 - 3340 cm-1, the newly generated C=O characteristic absorption peak is at 1743 cm-1, the special absorption peak of the ether bond is at 1116 cm-1, the Si-O-C characteristic absorption peak is at 1094 cm-1, and the Si-C characteristic absorption peak is at 892 cm-1.

[0028] Among them, the modified glass microspheres are prepared by the following method: Step B1: Immerse 1.3 g of glass microspheres in 20 ml of concentrated sulfuric acid, soak for 5 h, then wash them, and dry them under vacuum at 120 °C for 6 h to obtain the glass microsphere intermediate; Step B2: Ultrasonically disperse 1.1 g of the glass microsphere intermediate in 100 ml of 75% ethanol solution, add 0.3 g of silane coupling agent KH-560, ultrasonicate for 20 min, then continuously stir under oil bath conditions at 80 °C for 3 h. After the reaction is completed, centrifuge, separate, wash, and dry under vacuum to obtain the modified glass microsphere intermediate; Step B3: Ultrasonically disperse 1.4 g of the modified glass microsphere intermediate in 30 ml of toluene solution, then add 0.6 g of Amberlyst-15 and 1.3 g of 2,4-dihydroxybenzophenone to the solution, heat to 80 °C, react for 3 h. After the reaction is completed, filter, wash, and dry under vacuum to obtain the modified glass microspheres.

[0029] The infrared test comparison diagram of the glass microsphere intermediate and the modified glass microspheres is as Figure 2As shown in the infrared test diagram of the glass bead intermediate, there is a special absorption peak of O-H at 3216 cm-1, a characteristic absorption peak of Si-O-Si at 1096 cm-1. In the infrared test diagram of the modified glass beads, there is a characteristic absorption peak of O-H at 3312 cm-1, a characteristic absorption peak of keto C=O at 1627 cm-1, a characteristic absorption peak of the benzene ring skeleton at 1450 - 1600 cm-1, a characteristic absorption peak of C-O in the ester at 1258 cm-1, a characteristic absorption peak of Si-O-Si at 1112 cm-1, and a characteristic absorption peak of C-O-C at 1098 cm-1.

[0030] Example 2: A road marking functional coating for long-term retroreflection, by weight, includes the following raw materials: 50 parts of polyacrylic resin emulsion, 2 parts of defoamer tributyl phosphate, 4 parts of modified nano silicon carbide, 2 parts of modified glass beads, 8 parts of filler heavy calcium carbonate, 3 parts of curing agent aziridine, 3 parts of dispersant sodium polyacrylate, and 35 parts of deionized water.

[0031] The preparation method of the coating includes the following steps: Step 1: Mix the polyacrylic resin emulsion with the modified nano silicon carbide. After mixing, add the filler heavy calcium carbonate, modified glass beads, dispersant sodium polyacrylate, and deionized water into a mixer. After stirring evenly, add the defoamer tributyl phosphate and let it stand to form a premix. Step 2: Stir the premix evenly with the curing agent aziridine and store it at room temperature.

[0032] The preparation methods of the modified nano silicon carbide and the modified glass beads are the same as those in Example 1.

[0033] Example 3: A road marking functional coating for long-term retroreflection, by weight, includes the following raw materials: 60 parts of polyacrylic resin emulsion, 3 parts of defoamer tributyl phosphate, 5 parts of modified nano silicon carbide, 5 parts of modified glass beads, 10 parts of filler heavy calcium carbonate, 3 parts of curing agent aziridine, 5 parts of dispersant sodium polyacrylate, and 35 parts of deionized water.

[0034] The preparation method of the coating includes the following steps: Step 1: Mix the polyacrylic resin emulsion with the modified nano silicon carbide. After mixing, add the filler heavy calcium carbonate, modified glass beads, dispersant sodium polyacrylate, and deionized water into a mixer. After stirring evenly, add the defoamer tributyl phosphate and let it stand to form a premix. Step 2: Stir the premix evenly with the curing agent aziridine and store it at room temperature.

[0035] The preparation methods of the modified nano silicon carbide and the modified glass beads are the same as those in Example 1.

[0036] Comparative Example 1: A road marking functional coating for long-term reflection, by weight, includes the following raw materials: 60 parts of polyacrylic resin emulsion, 3 parts of defoamer tributyl phosphate, 5 parts of nano silicon carbide, 5 parts of modified glass beads, 10 parts of filler heavy calcium carbonate, 3 parts of curing agent aziridine, 5 parts of dispersant sodium polyacrylate, and 35 parts of deionized water. The preparation method of the coating includes the following steps: Step 1: Mix the polyacrylic resin emulsion with nano silicon carbide. After mixing, add the filler heavy calcium carbonate, modified glass beads, dispersant sodium polyacrylate, and deionized water into a mixer. After stirring evenly, add the defoamer tributyl phosphate and let it stand to form a premix; Step 2: Stir the premix evenly with the curing agent aziridine, and then store it at room temperature.

[0037] The preparation method of the modified glass beads is the same as that in Example 1.

[0038] Comparative Example 2: A road marking functional coating for long-term reflection, by weight, includes the following raw materials: 60 parts of polyacrylic resin emulsion, 3 parts of defoamer tributyl phosphate, 5 parts of modified glass beads, 10 parts of filler heavy calcium carbonate, 3 parts of curing agent aziridine, 5 parts of dispersant sodium polyacrylate, and 35 parts of deionized water. The preparation method of the coating includes the following steps: Step 1: Mix the polyacrylic resin emulsion with the filler heavy calcium carbonate. After mixing, add the dispersant sodium polyacrylate, modified glass beads, and deionized water into a mixer. After stirring evenly, add the defoamer tributyl phosphate and let it stand to form a premix; Step 2: Stir the premix evenly with the curing agent aziridine, and then store it at room temperature.

[0039] The preparation method of the modified glass beads is the same as that in Example 1.

[0040] Comparative Example 3: A road marking functional coating for long-term reflection, by weight, includes the following raw materials: 60 parts of polyacrylic resin emulsion, 3 parts of defoamer tributyl phosphate, 5 parts of modified nano silicon carbide, 5 parts of glass beads, 10 parts of filler heavy calcium carbonate, 3 parts of curing agent aziridine, 5 parts of dispersant sodium polyacrylate, and 35 parts of deionized water.

[0041] The preparation method of the coating includes the following steps: Step 1: Mix the polyacrylic resin emulsion with the modified nano silicon carbide. After mixing, add the filler heavy calcium carbonate, glass beads, dispersant sodium polyacrylate, and deionized water into a mixer. After stirring evenly, add the defoamer tributyl phosphate and let it stand to form a premix; Step 2: Stir the premix evenly with the curing agent aziridine, and then store it at room temperature.

[0042] The preparation method of the modified nano silicon carbide is the same as that in Example 1.

[0043] Comparative Example 4: A road marking functional coating for long-term retroreflection, by weight, comprises the following raw materials: 60 parts of polyacrylate resin emulsion, 3 parts of defoaming agent tributyl phosphate, 5 parts of modified nano silicon carbide, 10 parts of filler heavy calcium carbonate, 3 parts of curing agent aziridine, 5 parts of dispersant sodium polyacrylate, and 35 parts of deionized water. The preparation method of the coating comprises the following steps: Step 1: Mix the polyacrylate resin emulsion and the modified nano silicon carbide, and after mixing, add the filler heavy calcium carbonate, the dispersant sodium polyacrylate, and deionized water into a mixer, stir evenly, and then add the defoaming agent tributyl phosphate and let it stand to form a premix; Step 2: Stir the premix and the curing agent aziridine evenly, and then store it at room temperature.

[0044] The preparation method of the modified nano silicon carbide is the same as that in Example 1.

[0045] Comparative Example 5: A road marking functional coating for long-term retroreflection, by weight, comprises the following raw materials: 60 parts of polyacrylate resin emulsion, 3 parts of defoaming agent tributyl phosphate, 10 parts of filler heavy calcium carbonate, 3 parts of curing agent aziridine, 5 parts of dispersant sodium polyacrylate, and 35 parts of deionized water.

[0046] The preparation method of the coating comprises the following steps: Step 1: Mix the polyacrylate resin emulsion and the filler heavy calcium carbonate, and after mixing, add the dispersant sodium polyacrylate and deionized water into a mixer, stir evenly, and then add the defoaming agent tributyl phosphate and let it stand to form a premix; Step 2: Stir the premix and the curing agent aziridine evenly, and then store it at room temperature.

[0047] Performance testing: According to the industry standard of JT / T280-2004 road marking coatings, the abrasion resistance and the appearance of the coatings of the long-term retroreflection road marking functional coatings prepared in Examples 1-3 and Comparative Examples 1-5 of the present invention were tested. The method for aging the specimens was as follows: The prepared long-term retroreflection road marking functional coatings were continuously irradiated in a 1000W high-pressure mercury lamp ultraviolet aging chamber, and the time when phenomena such as bubbles, cracks, and peeling appeared on the coating were recorded to evaluate the anti-ultraviolet aging performance of the coatings. The test results are shown in the following table:

[0048] As can be seen from the above table, the coatings prepared in Examples 1-3 had the least weight loss after abrasion resistance testing, good abrasion resistance, no blistering, cracking, peeling and other phenomena within 1000 h, excellent UV resistance and good anti-aging performance.

[0049] In Comparative Example 1, ordinary nano-silicon carbide and modified glass microspheres were added during the preparation of the coating. After abrasion resistance testing, the weight loss was average, and its abrasion resistance was average. However, no blistering, cracking, peeling and other phenomena occurred within 1000 h, and its UV resistance was excellent and anti-aging performance was good.

[0050] In Comparative Example 2, only modified glass microspheres were added during the preparation of the coating. After abrasion resistance testing, the weight loss was relatively serious, and its abrasion resistance was poor. No blistering, cracking, peeling and other phenomena occurred within 1000 h, and its UV resistance was excellent and anti-aging performance was good.

[0051] In Comparative Example 3, modified silicon carbide and ordinary glass microspheres were added during the preparation of the coating, resulting in blistering, cracking, peeling and other phenomena at 723 h. Its UV resistance was poor and anti-aging performance was poor. After abrasion resistance testing, the weight loss was less and its abrasion resistance was good.

[0052] In Comparative Example 4, only modified silicon carbide was added during the preparation of the coating. Blistering occurred in the coating at 410 h. Therefore, its UV resistance was poor and anti-aging performance was not good. However, since there was still modified nano-silicon carbide in the coating, its abrasion resistance was good.

[0053] In Comparative Example 5, neither nano-silicon carbide nor glass microspheres were added during the preparation of the coating. Therefore, its abrasion resistance was the worst, UV resistance was the worst, and anti-aging performance was the worst.

[0054] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the specific embodiments described or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they shall fall within the protection scope of the present invention.

Claims

1. A road marking functional coating for long-term reflection, characterized in that, By weight, it includes the following raw materials: 40-60 parts of polyacrylic resin emulsion, 1-3 parts of defoamer, 3-5 parts of modified nano-silicon carbide, 1-3 parts of modified glass microspheres, 4-10 parts of filler, 1-3 parts of curing agent, 2-5 parts of dispersant, and 30-35 parts of deionized water.

2. The road marking functional coating for long-term reflection according to claim 1, wherein The defoamer is tributyl phosphate or fatty alcohol polyoxyethylene ether.

3. The road marking functional coating for long-term reflection according to claim 1, characterized in that, The filler is any one of quartz powder, heavy calcium carbonate, and magnesium hydroxide.

4. A road marking functional coating for long-term reflection according to claim 1, characterized in that, The dispersant is sodium polyacrylate or ammonium polyacrylate.

5. The road marking functional coating for long-term reflection according to claim 1, characterized in that, The preparation method of the modified nano-silicon carbide includes the following steps: Step A1: Immerse nano-silicon carbide powder in concentrated sulfuric acid, stir at 80-100 °C for 3-5 h, centrifuge and wash until neutral to obtain nano-silicon carbide intermediate, and vacuum dry for standby; Step A2: Disperse the nano-silicon carbide intermediate in toluene, then add maleic anhydride and a catalyst, react in an oil bath environment at 80-100 °C for 4-6 h, centrifuge to separate the solid material, wash and dry to obtain an intermediate product; Step A3: Disperse the intermediate product in N,N-dimethylformamide, ultrasonicate for 30-50 min, then add 4-dimethylaminopyridine and N,N'-dicyclohexylcarbodiimide, stir at 40-50 °C for 2-4 h, continue to add polyphenylene ether, after adding, raise the temperature to 120-130 °C, magnetically stir for 12-16 h, separate the product, wash and vacuum dry to obtain modified nano-silicon carbide.

6. The road marking functional coating for long-term reflection according to claim 5, wherein In Step A2, the mass ratio of the nano-silicon carbide intermediate to maleic anhydride is 8:1-2.

7. A road marking functional coating for long-term reflection according to claim 5, characterized in that, In Step A2, the catalyst is p-toluenesulfonic acid or methanesulfonic acid.

8. The road marking functional coating for long-term reflection according to claim 1, characterized in that, The preparation method of the modified glass microspheres includes the following steps: Step B1: Immerse glass microspheres in concentrated sulfuric acid, soak for 2-5 h, then wash, and then vacuum dry to obtain glass microsphere intermediate; Step B2: Ultrasonically disperse the glass microsphere intermediate in an ethanol solution, add silane coupling agent KH-560, ultrasonicate for 15-20 min, and then continuously stir at 60-80 °C in an oil bath for 3-5 h. After the reaction is completed, centrifuge, wash, and vacuum dry to obtain a modified glass microsphere intermediate; Step B3: Ultrasonically disperse the modified glass microsphere intermediate in a toluene solution, then add catalyst Amberlyst-15 and 2,4-dihydroxybenzophenone to the solution and heat to 60-80 °C, react for 3-5 h. After the reaction is completed, filter, wash, and vacuum dry to obtain modified glass microspheres.

9. A road marking functional coating for long-term reflection according to claim 8, characterized in that, In Step B2, the volume fraction of the ethanol solution is 65-75%.

10. The preparation method of a road marking functional coating for long-term reflection as described in claim 1, characterized in that, It includes the following steps: Step 1: Mix the polyacrylic resin emulsion and the modified nano-silicon carbide. After mixing, add the filler, modified glass microspheres, dispersant, and deionized water into a mixer, stir evenly, then add the defoamer and let it stand to form a premix; Step 2: Stir the premix and the curing agent evenly, and store at room temperature.

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