A low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material and its preparation method

Abstract

This invention relates to the field of cement materials technology, specifically disclosing a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material and its preparation method. The road marking material comprises the following components: 80-100 parts by weight of magnesium phosphate cement, 5-10 parts by weight of retarder, 2-5 parts by weight of ceramic powder, 0.8-1.2 parts by weight of borate-modified polyglycerol fatty acid ester, 10-15 parts by weight of glass microspheres, and 12-16 parts by weight of mixing water. The road marking material of this invention ensures that the magnesium phosphate cement maintains low adhesion, guaranteeing good fixation of the glass microspheres, while not affecting strength, thus ensuring that the formed reflective marking material has good wear resistance.

Description

Technical Field

[0001] This invention relates to the field of cement materials technology, specifically to a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material and its preparation method. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] As traffic infrastructure guiding pedestrian flow, road marking materials, through rational spatial allocation, visualization of road rules, timely risk warnings, and all-weather guidance, have become the cornerstone of modern road safety. Currently, commonly used road marking materials primarily use organic materials as binders, such as hot-melt petroleum resin-based road marking materials, solvent-based acrylic resin-based marking materials, and water-based road marking materials using water-based resin emulsions as binders. However, hot-melt marking materials require high-temperature melting during construction, which can release toxic gases at excessively high temperatures. Solvent-based marking materials release large amounts of VOCs during construction, easily causing environmental pollution. Water-based resins suffer from low bonding strength and poor wear resistance. Furthermore, organic road markings are not resistant to aging, exhibiting significant performance degradation during service.

[0004] Magnesium phosphate cement is a good road marking material due to its rapid hardening, high early strength, high bond strength, and good wear resistance. However, road marking materials often require the application of glass microspheres after pouring to improve visibility at night and in rainy or foggy weather. Although magnesium phosphate cement exhibits high fluidity at extremely low water-cement ratios, its high slurry viscosity makes it difficult for the applied glass microspheres to settle and embed into the slurry, resulting in insufficient adhesion between the magnesium phosphate cement and the glass microspheres. This leads to easy peeling off during service, significantly reducing visibility. While increasing the water-cement ratio of magnesium phosphate cement can reduce slurry viscosity, it reduces the density and strength of the hardened structure, thus affecting the secure fixation of the glass microspheres and the wear resistance of the structure. Therefore, current methods for preparing road marking materials using magnesium phosphate cement present a challenge in simultaneously achieving low slurry viscosity and high hardened body strength. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material and its preparation method. This method ensures that the magnesium phosphate cement has low adhesion, guaranteeing good fixation of the glass microspheres, while maintaining strength and ensuring the resulting reflective marking material has excellent wear resistance. Specifically, this invention discloses the following technical solution.

[0006] In a first aspect, the present invention provides a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material, the raw material composition of which includes the following components: 80-100 parts by weight of magnesium phosphate cement, 5-10 parts by weight of retarder, 2-5 parts by weight of ceramic powder, 0.8-1.2 parts by weight of borate polyglycerol fatty acid ester (B-PGFE), 10-15 parts by weight of glass microspheres, and 12-16 parts by weight of mixing water.

[0007] Further, the magnesium phosphate cement comprises: magnesium oxide and dihydrogen phosphate. Optionally, the ratio of magnesium oxide to dihydrogen phosphate is 65-80 parts by weight: 15-20 parts by weight.

[0008] Furthermore, the dihydrogen phosphate salt includes at least one of ammonium dihydrogen phosphate, potassium dihydrogen phosphate, etc.

[0009] Furthermore, the retarder includes at least one of triethanolamine, borax, citric acid, etc.

[0010] Furthermore, the glass microspheres have a particle size distribution between 0.5 and 1 mm. Optionally, the ceramic powder has a fineness ≥200 mesh. The ceramic powder can be made by grinding waste ceramics, floor tiles, etc.

[0011] Furthermore, the boronized polyglycerol fatty acid ester has a particle size ≤100μm.

[0012] Furthermore, the boronized polyglycerol fatty acid ester is prepared by the following method:

[0013] (1) Mix octaglycerol laurate, 2-formylphenylboronic acid, solvent and triethylamine and heat and stir to react. After the reaction is completed, raise the temperature and continue stirring. Cool the resulting reaction solution for later use.

[0014] (2) Adjust the pH of the reaction solution, then perform solid-liquid separation, wash the obtained filter residue, then combine the obtained washing liquid with the liquid phase obtained from the solid-liquid separation and evaporate to dryness, and finally dry and grind the obtained solid product to obtain the borate polyglycerol fatty acid ester (B-PGFE).

[0015] Further, in step (1), the ratio of octaglycerol laurate, 2-formylphenylboronic acid, solvent, and triethylamine is 4~8 parts by weight: 0.8~1.2 parts by weight: 5~10 parts by weight: 0.1~0.5 parts by weight.

[0016] Further, in step (1), the solvent includes at least one of toluene, ethylbenzene, p-xylene, etc.

[0017] Furthermore, in step (1), the heating temperature is 70~90℃, and the stirring reaction time is 5~10min.

[0018] Furthermore, in step (1), the temperature after heating is 95~115℃, and the stirring reaction continues for 10~15 minutes.

[0019] Further, in step (2), the pH of the reaction solution is adjusted to 6-8. This allows triethylamine and unreacted 2-formylphenylboronic acid to precipitate out in solid form, and also helps prevent decomposition of the product during subsequent drying. Optionally, at least one of sodium bicarbonate, sodium carbonate, potassium carbonate, etc., is used for pH adjustment.

[0020] Furthermore, in step (2), the evaporation temperature is 45~60℃, and the product is kept at this temperature until the weight of the solid product no longer changes.

[0021] Furthermore, in step (2), the drying temperature is 60~90℃ and the time is 40~60min.

[0022] Furthermore, the road marking material also includes 3-5 parts by weight of nano-SiO2@LDH. This is a core-shell structure formed by LDH (layered bimetallic hydroxide) coating the surface of SiO2 core particles. Optionally, the particle size of the nano-SiO2@LDH is 50-100 nm.

[0023] Furthermore, the preparation method of the nano-SiO2@LDH includes the following steps:

[0024] S1. Mix nano-SiO2 with an ethanol solution containing an acidic chelating agent, then sonicate the mixture. After the mixture is sonicated, separate the solid product and wash it to obtain activated nano-SiO2.

[0025] S2, the activated nano-SiO2 and Mg 2+ Source, Al 3+ The source and pH adjuster are added to water and mixed evenly. Then, the resulting alkaline mixture is subjected to a hydrothermal reaction. After completion, the solid product is separated and dried to obtain the nano-SiO2@LDH.

[0026] Further, in step S1, the mass fraction of the chelating agent in the ethanol solution is 0.3~0.8%. The mass fraction of the ethanol is not less than 95%. The amount of ethanol used is sufficient to disperse the nano-SiO2. Optionally, the chelating agent includes at least one of citric acid, oxalic acid, tartaric acid, etc.

[0027] Further, in step S1, the ultrasonic treatment time is 20-40 minutes. During this process, the chelating agent not only helps to remove metallic impurities from the SiO2 surface, but also increases the number and activity of hydroxyl groups (-OH) on the SiO2 surface through acid etching, promoting the adsorption and deposition of Mg²⁺ and Al³⁺ on the SiO2 surface, so as to form the core-shell structure formed by LDH coating the surface of the SiO2 core particles as described above.

[0028] Furthermore, in step S2, the activated nano-SiO2 and Mg 2+ Source, Al 3+ The ratio of source is 6~12g: 10~16g: 5~9g.

[0029] Further, in step S2, the Mg 2+ The sources include at least one of magnesium nitrate, magnesium sulfate, and magnesium chloride.

[0030] Further, in step S2, the Al 3+ The sources include at least one of aluminum nitrate, aluminum sulfate, and aluminum chloride.

[0031] Further, in step S2, the pH of the system is adjusted to 7.5-9.5 using the pH adjuster. The Mg²⁺ and Al³⁺ form a stable LDH layer with the OH⁻ provided by the pH adjuster, while ensuring that the SiO2 surface maintains a negative charge and tightly binds to the positively charged LDH to form a core-shell structure. Optionally, the pH adjuster includes at least one of urea, sodium bicarbonate, etc.

[0032] Further, in step S2, the hydrothermal reaction temperature is 120~140℃, and the reaction time is 4~10 hours. During this process, the pH adjuster undergoes hydrolysis to release OH⁻, gradually increasing the pH of the system. At the same time, the CO₃²⁻ generated by hydrolysis neutralizes the cations in the LDH layers, stabilizing the LDH layered structure.

[0033] Furthermore, in step S2, the drying temperature is 60~90℃ and the time is 8~12h.

[0034] In a first aspect, the present invention provides a method for preparing the low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material, comprising the following steps:

[0035] (i) First, mix the magnesium phosphate cement with borate polyglycerol fatty acid ester, then add the retarder and ceramic powder and mix, or add the retarder, ceramic powder and SiO2@LDH and mix, and finally add the mixing water and mix.

[0036] (ii) The cement-based slurry is coated onto the road surface, and the glass microspheres are evenly sprinkled on the cement-based slurry during the coating process. After hardening, magnesium phosphate cement-based road marking material is obtained.

[0037] Compared with the prior art, the technical solution of the present invention has at least the following beneficial effects:

[0038] When preparing road marking materials using magnesium phosphate cement, it is difficult to simultaneously achieve low slurry viscosity and strong bond strength in the hardened body. To address this, this invention utilizes a borate-modified polyglycerol fatty acid ester (B-PGFE) to modify magnesium phosphate cement. This modifies the cement while maintaining good fluidity, reducing viscosity and ensuring the resulting road markings retain good mechanical strength. Furthermore, it facilitates the settling and embedding of spread glass microspheres, improving the bond strength with the microspheres. This effectively overcomes the problem of glass microsphere peeling and significantly reduced visibility during service. This is because: firstly, the polyglycerol chains in the B-PGFE molecule are rich in dense hydroxyl groups, which can adsorb a large number of water molecules through hydrogen bonding, thereby forming a dynamic "bound water layer" on the surface of the magnesium phosphate cement particles. When the components of the magnesium phosphate cement-based pavement marking material are mixed, the "bound water layer" on the surface of the magnesium phosphate cement particles repels each other, generating a strong steric hindrance force. This effectively prevents the dense accumulation and friction of the particles, providing excellent physical lubrication, significantly reducing yield stress and plastic viscosity, thus facilitating the embedding of glass microspheres and the formation of denser, more uniform hydration products. On the other hand, under the action of spreading force and vibration during subsequent construction, the hydrogen bonds are broken, releasing water molecules from the dynamic "bound water layer," thereby improving the wettability between magnesium phosphate cement particles, ensuring the fluidity of the magnesium phosphate cement slurry, and also facilitating the embedding of subsequently spread glass microspheres. On the other hand, because B-PGFE contains both hydrophilic polyglycerol head groups and hydrophobic aliphatic tail chains, when it is added to magnesium phosphate cement slurry, the hydrophilic polyglycerol head groups tend to move into the slurry interior, while the hydrophobic aliphatic tail chains move away from the slurry and aggregate at the slurry-air interface, forming a directional arrangement. The continuous accumulation of aliphatic tail chains forms a hydrophobic film, reducing the internal attraction on the slurry surface and lowering the surface tension, thereby reducing the slurry viscosity. Simultaneously, the boric acid groups on B-PGFE can form BO-Mg coordination bonds with magnesium phosphate cement, playing a certain retarding role and allowing the magnesium phosphate cement slurry to maintain good fluidity and workability for a longer period.

[0039] In addition, the magnesium phosphate cement-based pavement marking material of the present invention also incorporates a core-shell structured SiO2@LDH. The layered structure of its LDH outer shell is rich in hydroxyl groups, enabling it to adsorb water molecules while also reacting with the Mg in the magnesium phosphate cement. 2+Coordination bonds are formed, increasing the density of the magnesium phosphate cement matrix and thus improving the wear resistance of the road markings. As the hydration process of the magnesium phosphate cement progresses, the pH of the system rises above 10 in the later stages. Under this environment, the LDH shell gradually decomposes and releases water, improving the fluidity of the magnesium phosphate cement slurry in the later stages of construction, reducing viscosity, and ensuring that the spread glass microspheres have sufficient embedding depth. Moreover, the nano-SiO2 inside the LDH shell is released after decomposition, which can play a nano-filling role in filling the voids in the magnesium phosphate cement matrix, helping to improve the mechanical strength of the formed road markings. Attached Figure Description

[0040] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0041] Figure 1 The image shows a boronized polyglycerol fatty acid ester sample prepared in Example 1 below.

[0042] Figure 2 The image shows the compressive strength test results of the magnesium phosphate cement-based slurry prepared in Example 1 below.

[0043] Figure 3 The plastic viscosity test graph is for the magnesium phosphate cement-based slurry prepared in Example 1 below.

[0044] Figure 4 The image shows a SiO2@LDH sample prepared in Example 2 below.

[0045] Figure 5 The image shows the compressive strength test results of the magnesium phosphate cement-based slurry prepared in Example 2 below.

[0046] Figure 6 The plastic viscosity test graph is for the magnesium phosphate cement-based slurry prepared in Example 2 below.

[0047] Figure 7 The image shows the compressive strength test results of the magnesium phosphate cement-based slurry prepared in Example 3 below.

[0048] Figure 8 The plastic viscosity test graph is for the magnesium phosphate cement-based slurry prepared in Example 3 below.

[0049] Figure 9 The image shows the compressive strength test results of the magnesium phosphate cement-based slurry prepared in Example 4 below.

[0050] Figure 10 The image shows the compressive strength test results of the magnesium phosphate cement-based slurry prepared in Example 5 below. Detailed Implementation

[0051] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer.

[0052] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as those skilled in the art. All reagents and raw materials used in this invention are readily available through conventional means, and unless otherwise specified, they shall be used in accordance with conventional methods in the art or as per the product instructions.

[0053] Furthermore, any methods and materials similar to or equivalent to those described herein can be applied to the method of this invention. The technical solution of this invention will now be further described in conjunction with the accompanying drawings and specific embodiments. Example

[0054] The preparation of a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material includes the following steps:

[0055] (1) Preparation of boronized polyglycerol fatty acid esters:

[0056] (i) Mix octaglycerol laurate, 2-formylphenylboronic acid, toluene, and triethylamine in a ratio of 5 parts by weight: 1.2 parts by weight: 5 parts by weight: 0.1 parts by weight. Heat the mixture to 85°C for 5 minutes under light-protected conditions, then heat it to 105°C for 10 minutes, stirring continuously with a magnetic force throughout the heating process. After completion, cool the resulting reaction solution to room temperature for later use.

[0057] (ii) The pH of the reaction solution was adjusted to 6.5 using sodium bicarbonate. The reaction solution was then filtered, and the resulting residue was washed with toluene. The washing liquid was combined with the filtrate obtained from the filtration and poured into a rotary evaporator. Residual toluene was removed by vacuum evaporation at 50°C. The resulting solid product was then vacuum dried at 75°C for 55 min. The solid product was then ground and sieved to obtain borate-modified polyglycerol fatty acid esters (e.g., with a particle size ≤100 μm) Figure 1 (As shown), for later use.

[0058] (2) Weigh the following components in the following proportions: 90 parts by weight of magnesium phosphate cement, 7.5 parts by weight of retarder (triethanolamine), 3 parts by weight of ceramic powder, 1.0 part by weight of borate-modified polyglycerol fatty acid ester in this embodiment, 12 parts by weight of glass microspheres, and 14 parts by weight of mixing water. The magnesium phosphate cement is prepared by mixing reburned magnesium oxide powder and potassium dihydrogen phosphate in a ratio of 70 parts by weight to 18 parts by weight. The particle size distribution of the glass microspheres is between 0.5 and 1 mm, and the fineness of the ceramic powder is 200 mesh.

[0059] (3) First, mix the magnesium phosphate cement with borate polyglycerol fatty acid ester and stir for 3 minutes. Then add the retarder and ceramic powder and stir for 1.5 minutes. Finally, add the mixing water and stir for 30 seconds to obtain magnesium phosphate cement-based slurry.

[0060] (4) The cement-based slurry is coated on the asphalt pavement substrate, and the glass microspheres are evenly sprinkled on the cement-based slurry at the same time, with the thickness controlled between 1.5 and 2 mm. After hardening, magnesium phosphate cement-based pavement marking material is obtained.

[0061] Performance Testing: 1. The fluidity of the magnesium phosphate cement-based slurry prepared in step (3) of this embodiment was tested according to JT / T 280-2022 "Road Marking Paint". 2. The compressive strength (e.g., ...) of the magnesium phosphate cement-based slurry prepared in step (3) of this embodiment was tested according to GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)". Figure 2 (As shown). 3. Test the plastic viscosity (e.g., ...) of the magnesium phosphate cement-based slurry prepared in step (3) of this embodiment according to GB / T9269-2009 "Determination of Viscosity of Coatings". Figure 3 (As shown). 4. The abrasion resistance of the marking material prepared in step (4) of this embodiment was tested according to JT / T 280-2022 "Road Marking Paint" standard. The test results are shown in the table below:

[0062]

[0063] Example 2: Preparation of a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material, comprising the following steps:

[0064] (1) Preparation of boronized polyglycerol fatty acid esters:

[0065] (i) Octaglycerol laurate, 2-formylphenylboronic acid, toluene, and triethylamine were mixed in a ratio of 4 parts by weight: 0.8 parts by weight: 7 parts by weight: 0.3 parts by weight. The mixture was heated to 90°C and held for 8 minutes under light-protected conditions, and then heated to 115°C and held for 12 minutes. During the above-mentioned holding process, the mixture was continuously stirred magnetically. After completion, the resulting reaction solution was cooled to room temperature for later use.

[0066] (ii) The pH of the reaction solution was adjusted to 6 using sodium bicarbonate. The reaction solution was then filtered, and the resulting filter residue was washed with toluene. The washing liquid was then combined with the filtrate obtained from the filtration and poured into a rotary evaporator. Residual toluene was removed by vacuum evaporation at 45°C. The resulting solid product was then dried under vacuum at 60°C for 60 min. The solid product was then ground and sieved to obtain borate-modified polyglycerol fatty acid esters with a particle size ≤100 μm, which were then set aside for later use.

[0067] (2) The preparation of nano-SiO2@LDH includes the following steps:

[0068] S1. Mix nano-SiO2 with anhydrous ethanol solution containing 0.3 wt.% citric acid, then sonicate for 20 min. After completion, centrifuge to separate the solid product, wash with water, and dry to obtain activated nano-SiO2.

[0069] S2. The activated nano-SiO2, magnesium nitrate, and aluminum nitrate were added to water in a ratio of 6g:10g:5g and stirred until homogeneous. Urea was then added to adjust the pH of the system to 9.5. The resulting alkaline mixture was then heated to 140℃ for a hydrothermal reaction for 4 hours. After completion, the solid product was separated by centrifugation and vacuum dried at 60℃ for 12 hours to obtain nano-SiO2@LDH. Figure 4 As shown.

[0070] (3) Weigh the following components in the following proportions: 100 parts by weight of magnesium phosphate cement, 10 parts by weight of retarder (borax), 5 parts by weight of ceramic powder, 1.2 parts by weight of borate-modified polyglycerol fatty acid ester (in this embodiment), 15 parts by weight of glass microspheres, 5 parts by weight of nano-SiO2@LDH (in this embodiment), and 16 parts by weight of mixing water. The magnesium phosphate cement is prepared by mixing reburned magnesium oxide powder and potassium dihydrogen phosphate in a ratio of 65 parts by weight to 15 parts by weight. The glass microspheres have a particle size distribution between 0.5 and 1 mm, and the ceramic powder has a fineness of 300 mesh.

[0071] (4) First, mix the magnesium phosphate cement with borate polyglycerol fatty acid ester and stir for 3 minutes. Then, add the retarder, ceramic powder, and nano SiO2@LDH and stir for 1.5 minutes. Finally, add the mixing water and stir for 30 seconds to obtain magnesium phosphate cement-based slurry.

[0072] (5) The cement-based slurry is coated on the asphalt pavement substrate, and the glass microspheres are evenly sprinkled on the cement-based slurry at the same time, with the thickness controlled between 1.5 and 2 mm. After hardening, magnesium phosphate cement-based pavement marking material is obtained.

[0073] Performance testing: The same methods as in Example 1 above were used to test various performance indicators of the magnesium phosphate cement-based slurry and magnesium phosphate cement-based pavement marking material prepared in this example (wherein, the compressive strength and plastic viscosity tests are as follows). Figure 5 , Figure 6 (As shown), the results are shown in the table below:

[0074]

[0075] Example 3: Preparation of a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material, comprising the following steps:

[0076] (1) Preparation of boronized polyglycerol fatty acid esters:

[0077] (i) Mix octaglycerol laurate, 2-formylphenylboronic acid, ethylbenzene, and triethylamine in a ratio of 8 parts by weight: 1 part by weight: 10 parts by weight: 0.5 parts by weight. Heat the mixture to 70°C for 10 minutes under light-protected conditions, then heat it to 95°C for 15 minutes, stirring continuously with a magnetic force throughout the heating process. After completion, cool the resulting reaction solution to room temperature for later use.

[0078] (ii) The pH of the reaction solution was adjusted to 8 using sodium carbonate. The reaction solution was then filtered, and the resulting filter residue was washed with ethylbenzene. The washing liquid was then combined with the filtrate obtained from the filtration and poured into a rotary evaporator. Residual ethylbenzene was removed by vacuum evaporation at 60°C. The resulting solid product was then vacuum dried at 90°C for 40 min. The solid product was then ground and sieved to obtain borate-modified polyglycerol fatty acid esters with a particle size ≤100 μm, which were then set aside for later use.

[0079] (2) The preparation of nano-SiO2@LDH includes the following steps:

[0080] S1. Mix nano-SiO2 with anhydrous ethanol solution containing 0.8 wt.% tartaric acid, then sonicate for 40 min. After completion, centrifuge to separate the solid product, wash with water, and dry to obtain activated nano-SiO2.

[0081] S2. The activated nano-SiO2, magnesium sulfate, and aluminum sulfate were added to water in a ratio of 12g:16g:9g and stirred until homogeneous. Sodium bicarbonate was then added to adjust the pH of the system to 7.5. The resulting alkaline mixture was then heated to 120°C for a hydrothermal reaction for 10 hours. After completion, the solid product was separated by centrifugation and vacuum dried at 90°C for 8 hours to obtain nano-SiO2@LDH.

[0082] (3) Weigh the following components in the following proportions: 80 parts by weight of magnesium phosphate cement, 5 parts by weight of retarder (citric acid), 2 parts by weight of ceramic powder, 0.8 parts by weight of borate polyglycerol fatty acid ester (in this embodiment), 10 parts by weight of glass microspheres, 3 parts by weight of nano-SiO2@LDH (in this embodiment), and 12 parts by weight of mixing water. The magnesium phosphate cement is prepared by mixing recalcined magnesium oxide powder and ammonium dihydrogen phosphate in a ratio of 80 parts by weight to 20 parts by weight. The particle size distribution of the glass microspheres is between 0.5 and 1 mm, and the fineness of the ceramic powder is 350 mesh.

[0083] (4) First, mix the magnesium phosphate cement with borate polyglycerol fatty acid ester and stir for 3 minutes. Then, add the retarder, ceramic powder, and nano SiO2@LDH and stir for 1.5 minutes. Finally, add the mixing water and stir for 30 seconds to obtain magnesium phosphate cement-based slurry.

[0084] (5) The cement-based slurry is coated on the asphalt pavement substrate, and the glass microspheres are evenly sprinkled on the cement-based slurry at the same time, with the thickness controlled between 1.5 and 2 mm. After hardening, magnesium phosphate cement-based pavement marking material is obtained.

[0085] Performance testing: The same methods as in Example 1 above were used to test various performance indicators of the magnesium phosphate cement-based slurry and magnesium phosphate cement-based pavement marking material prepared in this example (wherein, the compressive strength and plastic viscosity tests are as follows). Figure 7 , Figure 8 (As shown), the results are shown in the table below:

[0086]

[0087] Example 4: Preparation of a magnesium phosphate cement-based road marking material, comprising the following steps:

[0088] (1) Weigh the following components in the following proportions: 90 parts by weight of magnesium phosphate cement, 7.5 parts by weight of retarder (triethanolamine), 3 parts by weight of ceramic powder, 12 parts by weight of glass microspheres, and 14 parts by weight of mixing water. The magnesium phosphate cement is made by mixing reburned magnesium oxide powder and potassium dihydrogen phosphate in a ratio of 70 parts by weight to 18 parts by weight. The particle size of the glass microspheres is between 0.5 and 1 mm, and the fineness of the ceramic powder is 200 mesh.

[0089] (2) Mix the magnesium phosphate cement with the retarder and ceramic powder and stir for 1.5 min. Finally, add the mixing water and stir for 30 s to obtain magnesium phosphate cement-based slurry.

[0090] (3) The cement-based slurry is coated on the asphalt pavement substrate, and the glass microspheres are evenly sprinkled on the cement-based slurry at the same time, with the thickness controlled between 1.5 and 2 mm. After hardening, magnesium phosphate cement-based pavement marking material is obtained.

[0091] Performance testing: The same methods as in Example 1 above were used to test various performance indicators (compressive strength test, etc.) of the magnesium phosphate cement-based slurry and magnesium phosphate cement-based pavement marking material prepared in this example. Figure 9 (As shown), the results are shown in the table below:

[0092]

[0093] Example 5: Preparation of a magnesium phosphate cement-based pavement marking material, the same as in Example 1 above, except that the product prepared by the following method replaces the boronized polyglycerol fatty acid ester described in Example 1, specifically including the following steps:

[0094] (i) Mix octaglycerol laurate, toluene, and triethylamine in a ratio of 5 parts by weight: 5 parts by weight: 0.1 parts by weight. Heat the mixture to 85°C for 5 minutes under light-protected conditions, then heat it to 105°C for 10 minutes, stirring continuously with a magnetic force during the heating process. After completion, cool the resulting reaction solution to room temperature for later use.

[0095] (ii) The pH of the reaction solution was adjusted to 6.5 using sodium bicarbonate. The reaction solution was then filtered, and the resulting filter residue was washed with toluene. The washing liquid was then combined with the filtrate obtained from the filtration and poured into a rotary evaporator. Residual toluene was removed by vacuum evaporation at 50°C. The resulting solid product was then vacuum dried at 75°C for 55 min. The solid product was then ground and sieved to obtain a product with a particle size ≤100 μm.

[0096] Performance testing: The same methods as in Example 1 above were used to test various performance indicators of the magnesium phosphate cement-based slurry and magnesium phosphate cement-based pavement marking material prepared in this example (wherein, the compressive strength test is as follows). Figure 10 (As shown), the results are shown in the table below:

[0097]

[0098] Example 6: Preparation of a magnesium phosphate cement-based road marking material, comprising the following steps:

[0099] (1) Mix nano-SiO2 with anhydrous ethanol solution containing 0.3 wt.% citric acid, then sonicate for 20 min. After completion, centrifuge to separate the solid product, wash with water, and dry to obtain activated nano-SiO2 for later use.

[0100] (2) Weigh the following components in the following proportions: 100 parts by weight of magnesium phosphate cement, 10 parts by weight of retarder (borax), 5 parts by weight of ceramic powder, 1.2 parts by weight of borate polyglycerol fatty acid ester from Example 2 above, 15 parts by weight of glass microspheres, 5 parts by weight of activated nano-SiO2 from this example, and 16 parts by weight of mixing water. The magnesium phosphate cement is prepared by mixing reburned magnesium oxide powder and potassium dihydrogen phosphate in a ratio of 65 parts by weight to 15 parts by weight. The glass microspheres have a particle size distribution between 0.5 and 1 mm, and the ceramic powder has a fineness of 300 mesh.

[0101] (3) First, mix the magnesium phosphate cement with borate polyglycerol fatty acid ester and stir for 3 minutes. Then, add the retarder, ceramic powder and activated nano-SiO2 and stir for 1.5 minutes. Finally, add the mixing water and stir for 30 seconds to obtain magnesium phosphate cement-based slurry.

[0102] (4) The cement-based slurry is coated on the asphalt pavement substrate, and the glass microspheres are evenly sprinkled on the cement-based slurry at the same time, with the thickness controlled between 1.5 and 2 mm. After hardening, magnesium phosphate cement-based pavement marking material is obtained.

[0103] Performance testing: The performance indicators of the magnesium phosphate cement-based slurry and magnesium phosphate cement-based pavement marking material prepared in this embodiment were tested using the same method as in Example 1 above. The results are shown in the table below:

[0104]

[0105] Example 7: Preparation of a magnesium phosphate cement-based road marking material, the same as in Example 3 above, except that the nano-SiO2@LDH in this example is prepared using the following steps:

[0106] S1. After dispersing nano-SiO2 in anhydrous ethanol solution and mixing, ultrasonic treatment was performed for 40 min. After completion, the solid product was separated by centrifugation and dried to obtain pretreated nano-SiO2.

[0107] S2. The pretreated nano-SiO2, magnesium sulfate, and aluminum sulfate were added to water in a ratio of 12g:16g:9g and stirred until homogeneous. Sodium bicarbonate was then added to adjust the pH of the system to 7.5. The resulting alkaline mixture was then heated to 120°C for a hydrothermal reaction for 10 hours. After completion, the solid product was separated by centrifugation and vacuum dried at 90°C for 8 hours to obtain nano-SiO2@LDH.

[0108] Performance testing: The performance indicators of the magnesium phosphate cement-based slurry and magnesium phosphate cement-based pavement marking material prepared in this embodiment were tested using the same method as in Example 1 above. The results are shown in the table below:

[0109]

[0110] Example 8: Preparation of a low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material, similar to Example 2 above, except that the product prepared by the following method in this example replaces the nano-SiO2@LDH in Example 2 above, specifically including the following steps:

[0111] S1. Mix nano-SiO2 with anhydrous ethanol solution containing 0.3 wt.% citric acid, then sonicate for 20 min. After completion, centrifuge to separate the solid product, wash with water, and dry to obtain activated nano-SiO2.

[0112] S2. The activated nano-SiO2, magnesium nitrate, and aluminum nitrate were added to water in a ratio of 6g:10g:5g and stirred until homogeneous. The resulting mixture was then heated to 140°C for a hydrothermal reaction for 4 hours. After completion, the solid product was separated by centrifugation and dried under vacuum at 60°C for 12 hours to obtain the final product.

[0113] Performance testing: The performance indicators of the magnesium phosphate cement-based slurry and magnesium phosphate cement-based pavement marking material prepared in this embodiment were tested using the same method as in Example 1 above. The results are shown in the table below:

[0114]

[0115] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A low-viscosity, high-wear-resistant magnesium phosphate cement-based road marking material, characterized in that, The mixture comprises the following components: 80-100 parts by weight of magnesium phosphate cement, 5-10 parts by weight of retarder, 2-5 parts by weight of ceramic powder, 0.8-1.2 parts by weight of borate-modified polyglycerol fatty acid ester, 10-15 parts by weight of glass microspheres, and 12-16 parts by weight of mixing water; the borate-modified polyglycerol fatty acid ester is prepared by the following method: (1) Mix octaglycerol laurate, 2-formylphenylboronic acid, solvent and triethylamine and heat and stir to react. After the reaction is completed, raise the temperature and continue stirring to react. Cool the resulting reaction solution for later use. The solvent includes at least one of toluene, ethylbenzene and p-xylene. (2) Adjust the pH of the reaction solution, then perform solid-liquid separation, wash the obtained filter residue, then combine the obtained washing liquid with the liquid phase obtained from the solid-liquid separation and evaporate to dryness, and finally dry and grind the obtained solid product to obtain the borate polyglycerol fatty acid ester.

2. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to claim 1, characterized in that, The magnesium phosphate cement comprises magnesium oxide and dihydrogen phosphate in a ratio of 65-80 parts by weight to 15-20 parts by weight.

3. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to claim 1, characterized in that, The retarder includes at least one of triethanolamine, borax, and citric acid. Alternatively, the glass microspheres may have a particle size distribution between 0.5 and 1 mm. Alternatively, the fineness of the ceramic powder is ≥200 mesh; Alternatively, the boronized polyglycerol fatty acid ester may have a particle size ≤100μm.

4. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to claim 1, characterized in that, In step (1), the ratio of octaglycerol laurate, 2-formylphenylboronic acid, solvent, and triethylamine is 4-8 parts by weight: 0.8-1.2 parts by weight: 5-10 parts by weight: 0.1-0.5 parts by weight; Alternatively, in step (1), the heating temperature is 70~90℃ and the stirring reaction time is 5~10min; Alternatively, in step (1), the temperature after heating is 95~115℃, and the stirring reaction continues for 10~15 minutes.

5. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to claim 1, characterized in that, In step (2), the pH of the reaction solution is adjusted to 6-8; Alternatively, at least one of sodium bicarbonate, sodium carbonate, and potassium carbonate may be used to adjust the pH. Alternatively, in step (2), the evaporation temperature is 45~60℃, and the product is kept at this temperature until the weight of the solid product no longer changes. Alternatively, in step (2), the drying temperature is 60~90℃ and the time is 40~60min.

6. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to any one of claims 1-5, characterized in that, The road marking material also includes 3-5 parts by weight of nano-SiO2@LDH; which is a core-shell structure formed by LDH coating the surface of SiO2 core particles.

7. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to claim 6, characterized in that, The preparation method of the nano-SiO2@LDH includes the following steps: S1. Nano-SiO2 is mixed with an ethanol solution containing an acidic chelating agent, and then subjected to ultrasonic treatment. After completion, the solid product is separated and washed to obtain activated nano-SiO2. The chelating agent includes at least one of citric acid, oxalic acid, and tartaric acid. S2, the activated nano-SiO2 and Mg 2+ Source, Al 3+ The source and pH adjuster are added to water and mixed thoroughly. The resulting alkaline mixture is then subjected to a hydrothermal reaction at 120-140℃ for 4-10 hours. After completion, the solid product is separated and dried to obtain the nano-SiO2@LDH; wherein: the Mg... 2+ The source includes at least one of magnesium nitrate, magnesium sulfate, and magnesium chloride, Al 3+ The source includes at least one of aluminum nitrate, aluminum sulfate, and aluminum chloride, and the pH adjuster includes at least one of urea and sodium bicarbonate.

8. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to claim 7, characterized in that, In step S1, the mass fraction of the chelating agent in the ethanol solution is 0.3~0.8%; Alternatively, in step S1, the mass fraction of the ethanol is not less than 95%; Alternatively, in step S1, the ultrasonic treatment time is 20-40 minutes.

9. The low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to claim 7, characterized in that, In step S2, the activated nano-SiO2 and Mg 2+ Source, Al 3+ The ratio of source is 6~12g: 10~16g: 5~9g; Alternatively, in step S2, the pH of the system is adjusted to 7.5~9.5 using the pH adjuster; Alternatively, in step S2, the drying temperature is 60~90℃ and the time is 8~12h. Alternatively, in step S2, the particle size of the nano-SiO2@LDH is 50~100 nm.

10. A method for preparing the low-viscosity, high-wear-resistant magnesium phosphate cement-based pavement marking material according to any one of claims 1-9, comprising the following steps: (i) First, mix the magnesium phosphate cement with borate polyglycerol fatty acid ester, then add the retarder and ceramic powder and mix well, or add the retarder, ceramic powder and SiO2@LDH and mix well, and finally add the mixing water and mix well. (ii) The cement-based slurry obtained in step (i) is coated onto the road surface, and the glass microspheres are evenly sprinkled on the cement-based slurry during the coating process. After hardening, magnesium phosphate cement-based road marking material is obtained.

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