A pavement embedded anti-skid marking paint, its preparation process and construction method

Abstract

The application discloses a pavement embedded antiskid marking paint, a preparation process and a construction method, and belongs to the technical field of paint preparation. Firstly, alumina is treated by a solution and calcined to obtain alumina loaded nano zinc oxide powder, then the alumina loaded nano zinc oxide powder is subjected to aminoization pretreatment and reaction with hydrochloric acid dopamine to obtain core-shell type composite powder, and the surface polydopamine shell layer of the core-shell type composite powder can enhance the bonding force with a matrix and buffer stress; POSS and fluorinated siloxane modified waterborne polyurethane are compounded through a polymerization reaction to obtain modified polyurethane with the properties of oil stain resistance, waterproofness, weather resistance, stain resistance and mechanical properties; finally, the modified polyurethane, the core-shell type composite powder, nano titanium dioxide, aggregates and additives are mixed and placed to obtain the pavement embedded antiskid marking paint, and the pavement embedded antiskid marking paint has the properties of high adhesion, weather resistance, wear resistance, antiskid and corrosion resistance.

Description

Technical Field

[0001] This invention belongs to the field of coating preparation technology, specifically relating to a road surface embedded anti-skid marking coating and its preparation process and construction method. Background Technology

[0002] Road markings are an indispensable element of road design, and their proper placement is crucial for improving traffic capacity, ensuring traffic safety, and efficiency. However, traditional road markings are limited by the paint composition, resulting in a smooth surface after curing. This can easily cause vehicles to skid in rainy or snowy weather, posing a safety hazard. As a result, anti-skid markings have emerged.

[0003] However, traditional anti-skid markings suffer from problems such as fragility, short lifespan, and high maintenance costs. Road-embedded anti-skid markings are embedded by milling grooves, which lowers the elevation, reduces damage from vehicle traffic and snow removal operations, extends service life, and reduces maintenance costs. The key to fully realizing the effect of this structure lies in the filling material—hot-melt marking paint, which has stringent requirements for sidewall adhesion, strong cohesion, filling properties, wear resistance, impact resistance, and resistance to harsh environments.

[0004] Chinese invention patent application CN117887316A discloses an anti-skid road marking paint and its manufacturing method. The method involves mixing a photoinitiator with a photocurable resin, then adding luminescent hollow glass microspheres, ethylene-vinyl acetate copolymer, polyurethane, and pigments to obtain the road marking paint. It has good elasticity and resilience, can effectively increase the surface roughness of road markings, improve the anti-skid performance of road markings, and address the problem of insufficient friction coefficient in current road markings.

[0005] However, under conditions of large temperature differences between day and night, the thermal expansion coefficients of polyurethane and asphalt pavement differ greatly, leading to the accumulation of interfacial stress. Especially when shrinking at low temperatures, it is easy to cause edge cracking or overall peeling, resulting in poor adhesion. Frequent heating and cooling causes the elastomer to lose its elasticity and crack, resulting in poor weather resistance. Summary of the Invention

[0006] The purpose of this invention is to solve the problem of coating failure under large diurnal temperature differences by providing a road embedded anti-skid marking coating and its preparation process and construction method. Alumina-loaded nano-zinc oxide powder is pretreated with amination and then reacted with dopamine hydrochloride to obtain a core-shell composite powder with a polydopamine shell on the surface. On the one hand, the polydopamine shell buffers stress through flexible deformation and enhances interfacial bonding through bidirectional chemical anchoring, alleviating stress accumulation caused by differences in thermal expansion coefficients and improving adhesion. On the other hand, the uniform dispersion of nano-zinc oxide and the protective effect of the polydopamine shell maintain the structural stability of the POSS composite fluorinated siloxane-modified waterborne polyurethane matrix, reducing the damage to its elasticity caused by thermal cycling and ensuring the coating's weather resistance.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] A preparation process for a road surface embedded anti-skid marking paint includes the following steps:

[0009] Step 1: Using zinc chloride as the zinc source, zinc hydroxide is deposited on the surface of alumina powder by alkaline precipitation. After pyrolysis, alumina-supported nano zinc oxide powder is obtained. After treatment with silane coupling agent KH550, an aminated composite powder is obtained. Then, polydopamine is used for coating to obtain a core-shell composite powder.

[0010] Step 2: Polymerize polytetrahydrofuran ether diol, isophorone diisocyanate, fluorinated siloxane, hydrophilic chain extender and POSS nanoparticles to obtain POSS composite fluorinated siloxane modified waterborne polyurethane.

[0011] Step 3: POSS composite fluorinated siloxane modified waterborne polyurethane, core-shell composite powder, nano titanium dioxide, plasticizer, fine aggregate, coarse aggregate, defoamer, leveling agent and deionized water are mixed and then cured to obtain road embedded anti-skid marking paint.

[0012] Furthermore, the preparation process of alumina-supported nano-zinc oxide powder is as follows:

[0013] Alumina powder was added to a 10 mg / L zinc chloride solution and stirred for 30-50 min. The pH was adjusted to 10 with sodium hydroxide solution, and the mixture was stirred for another 2-3 h. After centrifugation and filtration, the filter cake was washed 3-5 times with anhydrous ethanol, dried at 80-100℃, transferred to a muffle furnace, and calcined at 500-600℃ at a heating rate of 10℃ / min for 3-4 h under nitrogen protection. The mixture was then allowed to cool naturally to room temperature to obtain alumina-supported nano-zinc oxide powder.

[0014] Furthermore, the ratio of alumina powder to zinc dichloride solution is 1-2g: 500-1000mL.

[0015] Furthermore, the preparation process of the core-shell composite powder is as follows:

[0016] Alumina-supported nano-zinc oxide powder was added to anhydrous ethanol and sonicated for 20-30 min. Then, silane coupling agent KH550 was added, and the mixture was stirred at 70-80℃ for 3-4 h. After centrifugation, washing, and drying, the aminated composite powder was obtained. The aminated composite powder was added to deionized water, and the pH was adjusted to 8.5 with sodium hydroxide. Dopamine hydrochloride powder was added, and the mixture was stirred for 20-30 min. Then, anhydrous ethanol was added, and the mixture was stirred at 500-600 rpm for 20-24 h. After centrifugation for 8-10 min, the mixture was filtered, and the filter cake was washed with anhydrous ethanol 3-5 times and dried for 20-30 min to obtain the core-shell composite powder.

[0017] Furthermore, the ratio of alumina-supported nano zinc oxide powder, anhydrous ethanol, and silane coupling agent KH550 is 1-2g: 100-200mL: 0.01-0.02g.

[0018] Furthermore, the ratio of the amount of amination compound powder, deionized water, dopamine hydrochloride powder and anhydrous ethanol is 60-80mg: 100-120mL: 80-100mg: 50-80mL.

[0019] Furthermore, the preparation process of POSS composite fluorinated siloxane modified waterborne polyurethane is as follows:

[0020] Polytetrahydrofuran ether diol, isophorone diisocyanate, fluorinated hydroxyl-terminated polymer, and 2,2-dimethylolpropionic acid were added to a reactor and stirred at 70-80°C for 1-2 hours under nitrogen protection. Then, a catalyst, octaaminopropyl POSS, and 1,4-butanediol were added, and the mixture was stirred at 70-80°C for 2-3 hours. The temperature was then lowered to 30°C, and triethylamine was added. The mixture was stirred for 20-30 minutes, followed by the addition of deionized water. The mixture was stirred at 1500 rpm for 20-30 minutes, and acetone in the emulsion dispersion was removed by vacuum distillation to obtain POSS-modified waterborne polyurethane with fluorinated siloxane.

[0021] Furthermore, the ratio of polytetrahydrofuran ether diol, isophorone diisocyanate, fluorinated hydroxyl-terminated polymer, 2,2-dimethylolpropionic acid, catalyst, octaaminopropyl POSS, 1,4-butanediol, triethylamine, and deionized water is 22-26g: 16-20g: 4-5g: 2.45-3.2g: 5-8mg: 1-1.5g: 2.4-2.8g: 1.85-2g: 120-150mL.

[0022] Furthermore, the fluorinated hydroxyl-terminated polymer is any one of dihydroxy polymethyltrifluoropropylsiloxane and perfluoropolyether diol, and the catalyst is any one of dibutyltin dilaurate and zinc neodecanoate.

[0023] Furthermore, the preparation process of a road surface embedded anti-skid marking paint is as follows:

[0024] POSS composite fluorinated siloxane modified waterborne polyurethane, core-shell composite powder, nano titanium dioxide and plasticizer are added to a premixer and stirred at 500-600 rpm for 20-30 min. Then fine aggregate and coarse aggregate are added and stirred at 800-900 rpm for 20-30 min. Then defoamer, leveling agent and deionized water are added and stirred for another 20-30 min. After standing and curing for 20-30 min, a road embedded anti-skid marking paint is obtained.

[0025] Furthermore, the ratio of the amounts of the composite fluorinated siloxane modified waterborne polyurethane, core-shell composite powder, nano titanium dioxide, plasticizer, fine aggregate, coarse aggregate, defoamer, leveling agent and deionized water is 80-100g: 8-10g: 1.2-1.5g: 3-4g: 12-15g: 20-25g: 0.2-0.3g: 0.5-0.6g: 10-12mL.

[0026] Furthermore, the leveling agent is either an acrylate leveling agent or an organosilicon-polyether composite leveling agent.

[0027] This invention also provides a method for applying an embedded anti-skid marking paint to a road surface, characterized by the following steps:

[0028] Grooving is performed at the marked area, epoxy resin primer is sprayed, road embedded anti-skid marking paint is applied to the epoxy resin primer surface, glass microbeads are sprinkled, and it is allowed to cure naturally to obtain road embedded anti-skid markings.

[0029] The beneficial effects of this invention are:

[0030] 1. This invention prepares a road surface embedded anti-skid marking coating through a multi-step composite design. First, nano-zinc oxide is loaded onto alumina, achieving atomic-level dispersion and strong interfacial coupling of the nano-zinc oxide on the carrier surface, improving the catalytic activity and adsorption capacity of the composite powder, and enhancing its stability under high-temperature conditions. Then, through amination treatment with silane coupling agent KH550 and self-polymerization coating with dopamine, a highly adhesive polydopamine shell is constructed on the inorganic powder surface. This structure enhances the interfacial bonding between the filler and the polyurethane matrix, effectively inhibiting the catalytic degradation of polyurethane molecular chains by nano-zinc oxide. Simultaneously, the shell deformation buffers stress, reducing local stress concentration, allowing impact energy to be more evenly distributed throughout the coating, thus improving impact resistance and durability.

[0031] 2. In the polymer matrix design, this invention introduces octaaminopropyl POSS and dihydroxy polymethyltrifluoropropylsiloxane to achieve organic-inorganic hybrid reinforcement. Fluorinated siloxane segments migrate to the surface to form a low surface energy layer, giving the coating oil and water resistance. Meanwhile, the POSS structure improves the toughness, thermal stability and weather resistance of the material, so that the polyurethane matrix has both good mechanical properties and environmental resistance.

[0032] 3. In the coating formulation of this invention, a staged mixing process is used to uniformly combine core-shell composite powder, nano-titanium dioxide, coarse and fine aggregates with modified polyurethane, ensuring filler dispersion and coating integrity. The fine / coarse aggregates provide an embedded anti-slip structure, nano-titanium dioxide enhances photocatalytic self-cleaning ability, and leveling agents and defoamers optimize the film-forming quality during construction. This coating comprehensively improves anti-slip properties, mechanical strength, environmental stability, stain resistance, and durability, making it suitable for long-term road marking applications under complex road conditions. Detailed Implementation

[0033] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments in the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0034] Example 1: A road surface embedded anti-skid marking paint, prepared by the following steps:

[0035] S1: Add 1g of alumina powder to 500mL of 10mg / L zinc dichloride solution, stir for 30min, adjust the pH to 10 with sodium hydroxide solution, stir for another 2h, centrifuge, filter, wash the filter cake three times with anhydrous ethanol, dry at 80℃, transfer to a muffle furnace, calcine at 500℃ for 3h under nitrogen protection at a heating rate of 10℃ / min, and naturally cool to room temperature to obtain alumina-supported nano zinc oxide powder.

[0036] By adsorption-precipitation-pyrolysis, atomic-level dispersion and strong interfacial coupling of zinc oxide nanophase on alumina support are achieved, thereby improving the catalytic activity, adsorption performance and high-temperature stability of the composite powder.

[0037] S2: Add 1g of alumina-supported nano-zinc oxide powder to 100mL of anhydrous ethanol, sonicate for 20min, then add 0.01g of silane coupling agent KH550, stir at 70℃ for 3h, centrifuge, wash, and dry to obtain aminated composite powder; add 60mg of aminated composite powder to 100mL of deionized water, adjust the pH to 8.5 with sodium hydroxide, add 80mg of dopamine hydrochloride powder, stir for 20min, then add 50mL of anhydrous ethanol, stir at 500rpm for 20h, centrifuge for 8min, filter, wash the filter cake three times with anhydrous ethanol, and dry for 20min to obtain core-shell composite powder.

[0038] By pretreatment with silane coupling agent amination and then coating with polydopamine, a polydopamine organic shell with strong adhesion is constructed on the surface of inorganic functional powder. This enhances the interfacial bonding force between the functional filler and the polyurethane matrix and inhibits the catalytic degradation of polyurethane by nano zinc oxide. The shell buffers stress through deformation, reduces stress concentration, and allows the impact force to be transmitted more evenly throughout the matrix.

[0039] S3: 22g of polytetrahydrofuran ether diol, 16g of isophorone diisocyanate, 4g of dihydroxypolymethyltrifluoropropylsiloxane and 2.45g of 2,2-dimethylolpropionic acid were added to a reaction vessel and stirred at 70°C for 1 hour under nitrogen protection. Then, 5mg of dibutyltin dilaurate, 1g of octaaminopropyl POSS and 2.4g of 1,4-butanediol were added and stirred at 70°C for 2 hours. The temperature was then lowered to 30°C, and 1.85g of triethylamine was added and stirred for 20 minutes. Then, 120mL of deionized water was added and stirred at 1500rpm for 20 minutes. The acetone in the emulsion dispersion was then removed by vacuum distillation to obtain POSS composite fluorinated siloxane modified waterborne polyurethane.

[0040] Through polymerization, POSS is combined with fluorinated siloxane-modified waterborne polyurethane. The polymethyltrifluoropropylsiloxane segments migrate to the material surface to form a low surface energy layer, which has anti-oil and waterproof properties. Combined with the toughening and thermal stability of POSS, it has better weather resistance, anti-fouling properties and mechanical properties.

[0041] S4: Add 80g of POSS composite fluorinated siloxane modified waterborne polyurethane, 8g of core-shell composite powder, 1.2g of nano titanium dioxide and 3g of plasticizer to a premixer and stir at 500rpm for 20min. Then add 12g of fine aggregate and 20g of coarse aggregate and stir at 800rpm for 20min. Then add 0.2g of defoamer, 0.5g of acrylate leveling agent and 10mL of deionized water and continue stirring for 20min. Transfer to a curing tank and let stand for 20min to obtain a road embedded anti-skid marking paint.

[0042] Example 2: Based on Example 1, in step S3, dihydroxy polymethyltrifluoropropylsiloxane was replaced with perfluoropolyether diol, while the other steps remained unchanged, to prepare a road embedded anti-skid marking coating.

[0043] Example 3: A road surface embedded anti-skid marking paint, prepared by the following steps:

[0044] S1: Add 1.5g of alumina powder to 750mL of 10mg / L zinc dichloride solution, stir for 40min, adjust the pH to 10 with sodium hydroxide solution, stir for another 2.5h, centrifuge, filter, wash the filter cake 4 times with anhydrous ethanol, dry at 90℃, transfer to a muffle furnace, calcine at 550℃ for 3.5h under nitrogen protection with a heating rate of 10℃ / min, and allow to cool naturally to room temperature to obtain alumina-supported nano zinc oxide powder.

[0045] S2: Add 1.5g of alumina-supported nano-zinc oxide powder to 150mL of anhydrous ethanol, sonicate for 25min, then add 0.015g of silane coupling agent KH550, stir at 75℃ for 3.5h, centrifuge, wash, and dry to obtain aminated composite powder; add 70mg of aminated composite powder to 110mL of deionized water, adjust the pH to 8.5 with sodium hydroxide, add 90mg of dopamine hydrochloride powder, stir for 25min, then add 65mL of anhydrous ethanol, stir at 550rpm for 22h, centrifuge for 9min, filter, wash the filter cake with anhydrous ethanol 4 times, and dry for 25min to obtain core-shell composite powder.

[0046] S3: 24g of polytetrahydrofuran ether diol, 18g of isophorone diisocyanate, 4.5g of dihydroxypolymethyltrifluoropropylsiloxane and 2.825g of 2,2-dimethylolpropionic acid were added to a reaction vessel and stirred at 75°C for 1.5h under nitrogen protection. Then, 6.5mg of dibutyltin dilaurate, 1.25g of octaaminopropyl POSS and 2.6g of 1,4-butanediol were added and stirred at 75°C for 2.5h. The temperature was then lowered to 30°C, and 1.925g of triethylamine was added and stirred for 25min. Then, 135mL of deionized water was added and stirred at 1500rpm for 25min. The acetone in the emulsion dispersion was then removed by vacuum distillation to obtain POSS composite fluorinated siloxane modified waterborne polyurethane.

[0047] S4: Add 90g of POSS composite fluorinated siloxane modified waterborne polyurethane, 9g of core-shell composite powder, 1.35g of nano titanium dioxide and 3.5g of plasticizer to a premixer and stir at 550rpm for 25min. Then add 13.5g of fine aggregate and 22.5g of coarse aggregate and stir at 850rpm for 25min. Then add 0.25g of defoamer, 0.55g of acrylate leveling agent and 11mL of deionized water and continue stirring for 25min. Transfer to a curing tank and let stand for 25min to obtain a road embedded anti-skid marking paint.

[0048] Example 4: Based on Example 3, in step S3, dibutyltin dilaurate was replaced with zinc neodecanoate, while the other steps remained unchanged, to prepare a road surface embedded anti-skid marking coating.

[0049] Example 5: A road surface embedded anti-skid marking paint, prepared by the following steps:

[0050] S1: Add 2g of alumina powder to 1000mL of 10mg / L zinc dichloride solution, stir for 50min, adjust the pH to 10 with sodium hydroxide solution, stir for another 3h, centrifuge, filter, wash the filter cake 5 times with anhydrous ethanol, dry at 100℃, transfer to a muffle furnace, calcine at 600℃ for 4h under nitrogen protection at a heating rate of 10℃ / min, and cool naturally to room temperature to obtain alumina-supported nano zinc oxide powder.

[0051] S2: Add 2g of alumina-supported nano-zinc oxide powder to 200mL of anhydrous ethanol, sonicate for 30min, then add 0.02g of silane coupling agent KH550, stir at 80℃ for 4h, centrifuge, wash, and dry to obtain aminated composite powder; add 80mg of aminated composite powder to 120mL of deionized water, adjust the pH to 8.5 with sodium hydroxide, add 100mg of dopamine hydrochloride powder, stir for 30min, then add 80mL of anhydrous ethanol, stir at 600rpm for 24h, centrifuge for 10min, filter, wash the filter cake 5 times with anhydrous ethanol, and dry for 30min to obtain core-shell composite powder.

[0052] S3: 26g of polytetrahydrofuran ether diol, 20g of isophorone diisocyanate, 5g of dihydroxypolymethyltrifluoropropylsiloxane and 3.2g of 2,2-dimethylolpropionic acid were added to a reaction vessel and stirred at 80°C for 2 hours under nitrogen protection. Then, 8mg of dibutyltin dilaurate, 1.5g of octaaminopropyl POSS and 2.8g of 1,4-butanediol were added and stirred at 80°C for 3 hours. The temperature was then lowered to 30°C, and 2g of triethylamine was added and stirred for 30 minutes. Then, 150mL of deionized water was added and stirred at 1500rpm for 30 minutes. Finally, acetone in the emulsion dispersion was removed by vacuum distillation to obtain POSS composite fluorinated siloxane modified waterborne polyurethane.

[0053] S4: Add 100g of POSS composite fluorinated siloxane modified waterborne polyurethane, 10g of core-shell composite powder, 1.5g of nano titanium dioxide and 4g of plasticizer to a premixer and stir at 600rpm for 30min. Then add 15g of fine aggregate and 25g of coarse aggregate and stir at 900rpm for 30min. Then add 0.3g of defoamer, 0.6g of acrylate leveling agent and 12mL of deionized water and continue stirring for 30min. Transfer to a curing tank and let stand for 30min to obtain a road embedded anti-skid marking paint.

[0054] Example 6: Based on Example 5, in step S4, the acrylate leveling agent was replaced with an organosilicon-polyether composite leveling agent, while the other steps remained unchanged, to prepare a road surface embedded anti-skid marking coating.

[0055] The raw materials used in Examples 1-6 of this application are all commercially available products. The fine aggregate is any one of quartz sand, ceramic microspheres or other high-hardness mineral powders; the coarse aggregate is any one of sintered ceramic particles, corundum or alumina; and the groove depth at the location where the road markings are applied is 0.8-1.2 mm.

[0056] Comparative Example 1: The difference from Example 1 is that step S1 is omitted, and in step S2, alumina is used to replace alumina-loaded zinc oxide powder, while the other steps remain unchanged, to prepare a road surface embedded anti-skid marking coating.

[0057] Comparative Example 2: The difference from Example 1 is that dopamine hydrochloride powder is not added in step S2, and the core-shell composite powder in step S4 is replaced with the aminated composite powder prepared in step S2. The remaining steps remain unchanged, and a road embedded anti-skid marking coating is prepared.

[0058] Comparative Example 3: The difference from Example 1 is that octaaminopropyl POSS is not added in step S3 to prepare fluorinated siloxane-modified waterborne polyurethane. Instead, fluorinated siloxane-modified waterborne polyurethane is used to replace POSS composite fluorinated siloxane-modified waterborne polyurethane. The remaining steps remain unchanged, and a road embedded anti-skid marking coating is prepared.

[0059] Example 7: A method for applying an embedded anti-skid marking paint to a road surface, comprising the following steps:

[0060] Step 1: Use tools such as a sweeper and blower to sweep the road surface to remove dust and sand, and make grooves at the marked areas;

[0061] Step 2: Spray epoxy resin primer onto the groove base surface for 15-20 minutes. Transfer the road surface embedded anti-skid marking paint to the hopper of the marking vehicle and start applying it to the epoxy resin primer surface. The marking thickness should be consistent with the groove depth. Lightly sprinkle 0.4-0.6mm glass microbeads and allow it to cure naturally to obtain the road surface embedded anti-skid marking.

[0062] The road embedded anti-skid markings are obtained by applying any of the road embedded anti-skid marking coatings prepared in Examples 1-6 and Comparative Examples 1-3.

[0063] The road embedded anti-skid marking paint prepared in Examples 1, 3, 5 and Comparative Examples 1-3 was applied by brushing onto a steel test plate with dimensions of 50mm×120mm×(0.45-0.55)mm. The paint film thickness was controlled at (60±10) micrometers. The plate was dried for 48 hours under constant temperature and humidity conditions of (23±2)℃ and (50±5)% relative humidity, and then left to stand for 7 days to obtain experimental samples. The following performance tests were conducted:

[0064] Anti-slip test: The wet anti-slip test was carried out on the test samples in accordance with GB / 9263-2020 "Determination of anti-slip properties of anti-slip coatings". Each test sample was tested in 3 parallel tests and the average value was taken.

[0065] Abrasion resistance test: The abrasion resistance of the test specimens was determined using an abrasion tester in accordance with ASTM D4060-19, "Standard Test Method for Determining the Abrasion Resistance of Organic Coatings Using a Tiber Abrasion Tester".

[0066] Adhesion test: The adhesion of the test specimens was tested in accordance with GB / T5210-2006 "Paints and Varnishes - Pull-off Adhesion Test".

[0067] Corrosion resistance: The corrosion resistance of the test specimens was tested in accordance with GB / T1771-1991 standard;

[0068] Artificial weathering resistance test: The test samples were subjected to artificial weathering resistance testing according to GB / T14522-2008 "Artificial Weathering Test Method for Plastics, Coatings and Rubber Materials for Mechanical Industry Products - Fluorescent Ultraviolet Lamp". Five parallel tests were conducted on each sample plate, and the most frequent occurrence was taken as the result. The results were evaluated according to GB / T1766-2008 "Rating Method for Aging of Paint and Varnish Coatings", with grade 0 being the best and grade 5 the worst. The results are shown in Table 1.

[0069] Table 1 Performance test results of a type of road surface embedded anti-skid marking paint

[0070]

[0071] As can be seen from Table 1, the performance of the road embedded anti-skid marking coatings prepared in Examples 1, 3 and 5 of this invention is significantly better than that of the comparative examples.

[0072] In Comparative Example 1, the anti-slip coefficient and the static friction coefficient of the wet surface decreased significantly. This may be because nano zinc oxide was not loaded on the alumina surface. Loading nano zinc oxide, with its nano-sized protruding particles, can significantly increase the friction between the coating surface and the contact object. In addition, the hydroxyl groups on the alumina surface are highly hydrophilic and easily adsorb a large number of water molecules in the wet state to form a water film. The nano-sized protruding particles of nano zinc oxide can destroy the water film and further enhance the anti-slip properties of the coating surface.

[0073] Comparative Example 2 showed a significant decrease in weather resistance and corrosion resistance, possibly because the dopamine hydrochloride powder was not added, thus failing to form a core-shell composite powder. The polydopamine shell can effectively block external aging factors and corrosive media from penetrating into the coating.

[0074] The adhesion of Comparative Example 3 decreased significantly, possibly due to the absence of octaaminopropyl POSS. Octaaminopropyl POSS has a cage-like structure and contains multiple active amino groups in its molecule. Its amino groups can react chemically with the isocyanate groups in the polyurethane prepolymer to form covalent crosslinks, which improves the crosslinking density and structural integrity of the POSS-composite fluorinated siloxane-modified waterborne polyurethane matrix. Its amino groups are strongly polar groups, which can form strong hydrogen bonds or even chemical bonds with the hydroxyl and carboxyl groups of the road substrate, thereby improving the interfacial bonding force. The cage-like structure of POSS can increase the surface roughness of the coating substrate, synergistically improving the adhesion.

[0075] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. A preparation process for a road surface embedded anti-skid marking paint, characterized in that, Includes the following steps: Step 1: Using zinc chloride as the zinc source, zinc hydroxide is deposited on the surface of alumina powder by alkaline precipitation. After pyrolysis, alumina-supported nano zinc oxide powder is obtained. After treatment with silane coupling agent KH550, an aminated composite powder is obtained. Then, polydopamine is used for coating to obtain a core-shell composite powder. Step 2: Polymerize polytetrahydrofuran ether diol, isophorone diisocyanate, fluorinated siloxane, hydrophilic chain extender and POSS nanoparticles to obtain POSS composite fluorinated siloxane modified waterborne polyurethane. Step 3: POSS composite fluorinated siloxane modified waterborne polyurethane, core-shell composite powder, nano titanium dioxide, plasticizer, fine aggregate, coarse aggregate, defoamer, leveling agent and deionized water are stirred and mixed, and after standing and maturing, the road embedded anti-skid marking paint is obtained. The preparation process of the core-shell composite powder is as follows: Alumina-supported nano-zinc oxide powder was added to anhydrous ethanol and sonicated for 20-30 min. Then, silane coupling agent KH550 was added, and the mixture was stirred at 70-80℃ for 3-4 h. After centrifugation, washing, and drying, an aminated composite powder was obtained. The aminated composite powder was added to deionized water, and the pH was adjusted to 8.5 with sodium hydroxide. Dopamine hydrochloride powder was added, and the mixture was stirred for 20-30 min. Then, anhydrous ethanol was added, and the mixture was stirred at 500-600 rpm for 20-24 h. After centrifugation for 8-10 min, the mixture was filtered, and the filter cake was washed with anhydrous ethanol 3-5 times and dried for 20-30 min to obtain a core-shell composite powder. The preparation process of the POSS composite fluorinated siloxane modified waterborne polyurethane is as follows: Polytetrahydrofuran ether diol, isophorone diisocyanate, fluorinated hydroxyl-terminated polymer and 2,2-dimethylolpropionic acid were added to a reaction vessel and stirred at 70-80℃ for 1-2 hours under nitrogen protection. Then, catalyst, octaaminopropyl POSS and 1,4-butanediol were added and stirred for 2-3 hours. The mixture was then cooled to 30℃ and triethylamine was added. The mixture was stirred for 20-30 minutes and then deionized water was added. The mixture was stirred at 1500 rpm for 20-30 minutes and acetone was removed under reduced pressure to obtain POSS composite fluorinated siloxane modified waterborne polyurethane. The ratio of polytetrahydrofuran ether diol, isophorone diisocyanate, fluorinated hydroxyl-terminated polymer, 2,2-dimethylolpropionic acid, catalyst, octaaminopropyl POSS, 1,4-butanediol, triethylamine, and deionized water is 22-26g: 16-20g: 4-5g: 2.45-3.2g: 5-8mg: 1-1.5g: 2.4-2.8g: 1.85-2g: 120-150mL; The fluorinated hydroxyl-terminated polymer is any one of dihydroxy polymethyltrifluoropropylsiloxane and perfluoropolyether diol, and the catalyst is any one of dibutyltin dilaurate and zinc neodecanoate.

2. The preparation process of the road embedded anti-skid marking paint according to claim 1, characterized in that, The preparation process of the alumina-supported nano zinc oxide powder is as follows: Alumina powder was added to a 10 mg / L zinc chloride solution and stirred for 30-50 min. The pH was adjusted to 10 with sodium hydroxide solution, and the mixture was stirred for another 2-3 h. After centrifugation and filtration, the filter cake was washed 3-5 times with anhydrous ethanol, dried at 80-100℃, transferred to a muffle furnace, and calcined at 500-600℃ at a heating rate of 10℃ / min for 3-4 h under nitrogen protection. The mixture was then allowed to cool naturally to room temperature to obtain alumina-supported nano-zinc oxide powder.

3. The preparation process of a road surface embedded anti-skid marking paint according to claim 2, characterized in that, The ratio of alumina powder to zinc chloride solution is 1-2g: 500-1000mL.

4. The preparation process of the road embedded anti-skid marking paint according to claim 1, characterized in that, The ratio of alumina-supported nano zinc oxide powder, anhydrous ethanol, and silane coupling agent KH550 is 1-2g: 100-200mL: 0.01-0.02g; the ratio of amination-modified composite powder, deionized water, dopamine hydrochloride powder, and anhydrous ethanol is 60-80mg: 100-120mL: 80-100mg: 50-80mL.

5. The preparation process of a road surface embedded anti-skid marking paint according to claim 1, characterized in that, The ratio of the amount of the composite fluorinated siloxane modified waterborne polyurethane, core-shell composite powder, nano titanium dioxide, plasticizer, fine aggregate, coarse aggregate, defoamer, leveling agent and deionized water is 80-100g: 8-10g: 1.2-1.5g: 3-4g: 12-15g: 20-25g: 0.2-0.3g: 0.5-0.6g: 10-12mL; the leveling agent is any one of acrylate leveling agent and organosilicon-polyether composite leveling agent.

6. A road surface embedded anti-skid marking paint, prepared according to the preparation process of any one of claims 1-5.

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