Durable high-brightness road marking paint and preparation method thereof

Abstract

The present invention relates to the field of road marking paints, and in particular to a durable high-gloss road marking paint and a preparation method thereof, which are used to solve the problem that existing road marking paints have poor durability, are prone to fading, damage, and reduced reflective performance of road markings, thereby affecting driving safety. The durable high-gloss road marking paint uses a high-performance durable emulsion as a film-forming substance, which imparts good wear resistance and weather resistance to the coating film, making the road markings less susceptible to damage during long-term use and capable of maintaining the clarity and integrity of the road markings for a long time. Modified glass microspheres are added thereto, so that the coating film has excellent reflective properties, and the modified glass microspheres are easily evenly dispersed in the paint, so that the road markings can be clearly identified even at night or in low-light environments, significantly improving the visibility of the road markings and enhancing driving safety. Moreover, the preparation method is simple in process and easy to implement industrial production.

Description

Technical Field

[0001] The invention relates to the field of road marking paints, and in particular to a durable high-gloss road marking paint and a preparation method thereof. Background Art

[0002] With the continuous increase in traffic volume and vehicle speeds, the performance requirements for road marking paints are becoming increasingly higher. Road marking paints are mainly used on concrete or asphalt pavement and play a vital role in road traffic, guiding vehicles, regulating traffic order, and ensuring traffic safety.

[0003] Currently, road marking paints on the market are mainly composed of reflective glass beads, pavement bonding resins and additives. As the key reflective material in road marking paints, reflective glass beads have a direct impact on the reflective effect of the markings. However, the bonding strength between traditional reflective glass beads and pavement bonding resins is not strong, resulting in easy falling off during the coating process, which limits the service life and reflective performance of the road marking paints. In addition, pavement bonding resins are easily affected by factors such as vehicle running over, rain erosion, and ultraviolet radiation during long-term use, causing the markings to fade, wear, and reduce reflective performance, affecting driving safety.

[0004] Therefore, the development of a durable high-gloss road marking paint and a preparation method thereof is of great practical significance for improving the durability of road marking paint and maintaining the reflective effect for a long time. Summary of the Invention

[0005] In order to overcome the above technical problems, the purpose of the present invention is to provide a durable high-brightness road marking paint and a preparation method thereof, which solves the problem that existing road marking paints have poor durability, easily cause the markings to fade, be damaged, and have reduced reflective performance, thereby affecting driving safety.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A durable high-gloss road marking paint comprises the following components in parts by weight:

[0008] 25-30 parts of high-performance durable emulsion, 5-13 parts of modified glass microspheres, 1.1-1.5 parts of sodium lauryl sulfate, 0.5-0.7 parts of anti-settling and thickening thixotropic agent, 0.2-0.6 parts of defoaming agent, 0.2-0.6 parts of leveling agent and 0.1-0.3 parts of thickener;

[0009] Wherein, the high performance durable emulsion is prepared by the following steps:

[0010] Step a1: paraformaldehyde, potassium tert-butoxide, and tert-butanol are added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen is introduced for protection. The mixture is stirred at a temperature of 25-30° C. and a stirring rate of 200-300 r / min for 30-35 minutes. 2,6-di-tert-butylphenol is then added and the stirring reaction is continued for 4-5 hours. After the reaction is completed, the reaction product is poured into distilled water, and the solvent is then removed by rotary evaporation. The product is then recrystallized from n-hexane to obtain a hydroxymethyl hindered phenol intermediate.

[0011] Step a2: adding a hydroxymethyl hindered phenol intermediate, triethylamine, and dichloromethane to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel, stirring and reacting for 10-15 minutes at a temperature of -5-0°C and a stirring rate of 200-300 r / min, then adding acryloyl chloride solution dropwise while stirring, controlling the dropping rate to 1-2 drops / s, and continuing to stir and react for 7-8 hours under the condition of raising the temperature to 25-30°C after the addition is completed. After the reaction is completed, the reaction product is vacuum filtered, and the filtrate is washed with distilled water, hydrochloric acid solution, and sodium bicarbonate solution in sequence for 3-5 times, and then dried over anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then recrystallized with anhydrous ethanol to obtain a hindered phenol polymerization monomer;

[0012] Step a3: Methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol polymerization monomer, composite emulsifier, sodium bicarbonate and deionized water are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen is introduced. The mixture is stirred and reacted at a temperature of 25-30° C. and a stirring rate of 200-300 r / min for 20-30 minutes. Then, the temperature is raised to 85-90° C. and ammonium persulfate solution is added dropwise while stirring at a dropping rate of 1-2 drops / s. After the addition is completed, the stirring reaction is continued for 4-5 hours. After the reaction is completed, the reaction product is cooled to room temperature and then passed through a 200-300 mesh sieve to obtain a high-performance durable emulsion.

[0013] As a further embodiment of the present invention: the usage ratio of the paraformaldehyde, potassium tert-butoxide, tert-butanol and 2,6-di-tert-butylphenol in step a1 is 2.5-3.1 g: 0.13-0.17 g: 40-50 mL: 30 mmol.

[0014] As a further embodiment of the present invention: the usage ratio of the hydroxymethyl hindered phenol intermediate, triethylamine, dichloromethane and acryloyl chloride solution in step a2 is 10 mmol: 13-15 mmol: 40-50 mL: 10 mL.

[0015] As a further embodiment of the present invention, the acryloyl chloride solution in step a2 is a solution formed by dissolving acryloyl chloride in dichloromethane at a ratio of 11-12 mmol:10 mL; and the molar concentration of the hydrochloric acid solution and the sodium bicarbonate solution is 1 mol / L.

[0016] As a further embodiment of the present invention, the methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol polymerization monomer, composite emulsifier, sodium bicarbonate, deionized water and ammonium persulfate solution in step a3 are used in a ratio of 15-20 g: 15-20 g: 2.3-2.9 g: 5.2-7.6 g: 3.6-8.2 g: 1.5-4.5 g: 1.3-2.7 g: 0.3-0.5 g: 50-55 mL: 10-15 mL.

[0017] As a further embodiment of the present invention: the mass fraction of the ammonium persulfate solution in step a3 is 2.5%; the composite emulsifier is a mixture of OP-10 emulsifier and AEO-7 emulsifier in a mass ratio of 2:1.

[0018] As a further solution of the present invention: the modified glass microspheres are prepared by the following steps:

[0019] Step b1: adding glass microspheres and deionized water to a beaker, stirring and mixing at a temperature of 25-30°C and a stirring rate of 200-300 r / min for 20-30 minutes, then standing for 2-3 hours, collecting the upper layer of glass microspheres and placing them in a vacuum drying oven, and drying them at a temperature of 90-100°C for 2-3 hours to obtain flotation glass microspheres;

[0020] Step b2: adding the flotation glass microspheres, sodium hydroxide and deionized water to a three-necked flask equipped with a stirrer and a thermometer, stirring and reacting for 5-10 minutes at a temperature of 25-30° C. and a stirring rate of 200-300 r / min, then heating to 45-50° C. and continuing to stir and react for 4-5 hours. After the reaction is completed, the reaction product is cooled to room temperature and then vacuum filtered. The filter cake is washed with deionized water and anhydrous ethanol 3-5 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 90-100° C. for 3-4 hours to obtain pretreated glass microspheres;

[0021] Step b3: Add γ-mercaptopropyltriethoxysilane and ethanol solution to a three-necked flask equipped with an agitator and a thermometer, stir and react for 10-15 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min, then add pretreated glass microspheres and continue stirring and reacting for 4-5 hours under the condition of raising the temperature to 65-70°C. After the reaction is completed, the reaction product is cooled to room temperature and then vacuum filtered. The filter cake is washed with deionized water and anhydrous ethanol for 3-5 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 70-75°C for 2-3 hours to obtain modified glass microspheres.

[0022] As a further solution of the present invention: the usage ratio of the glass microspheres and deionized water in step b1 is 20 g:100-120 mL.

[0023] As a further solution of the present invention: the glass microspheres in step b1 are 3M hollow glass microspheres S28HS.

[0024] As a further solution of the present invention: the usage ratio of the flotation glass microspheres, sodium hydroxide and deionized water in step b2 is 10g:1.2-1.5g:100-110mL.

[0025] As a further solution of the present invention: the usage ratio of the γ-mercaptopropyltriethoxysilane, ethanol solution and pretreated glass microspheres in step b3 is 0.5-3.9 g:100-120 mL:10 g.

[0026] As a further solution of the present invention: the volume fraction of the ethanol solution in step b3 is 85-90%.

[0027] As a further solution of the present invention: a method for preparing a durable high-brightness road marking paint comprises the following steps:

[0028] Step 1: Weigh 25-30 parts of high-performance durable emulsion, 5-13 parts of modified glass microspheres, 1.1-1.5 parts of sodium lauryl sulfate, 0.5-0.7 parts of anti-settling thickening thixotropic agent, 0.2-0.6 parts of defoaming agent, 0.2-0.6 parts of leveling agent and 0.1-0.3 parts of thickener according to weight parts, and set aside;

[0029] Step 2: Add the high-performance durable emulsion, modified glass microspheres and sodium lauryl sulfate to a stirred tank, stir and react for 10-15 minutes at a temperature of 25-30°C and a stirring rate of 200-300 r / min, then raise the temperature to 85-90°C and continue stirring and reacting for 3-5 hours. After the reaction is completed, cool the reaction product to room temperature to obtain a durable high-gloss emulsion;

[0030] Step 3: Add the anti-settling thickening thixotropic agent, defoaming agent, leveling agent and thickener to the durable high-gloss emulsion, stir and react for 30-50 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min to obtain a durable high-gloss marking paint.

[0031] As a further solution of the present invention: the anti-settling thickening thixotropic agent is a polyamide wax slurry 4310-20X solvent-based coating anti-settling thickening thixotropic agent.

[0032] As a further solution of the present invention: the defoaming agent is tego810 aqueous defoaming agent.

[0033] As a further solution of the present invention: the leveling agent is a water-based leveling agent BYK-333.

[0034] As a further embodiment of the present invention: the thickener is DEURHEO WT-105A thickener.

[0035] Beneficial effects of the present invention:

[0036] The present invention discloses a durable high-gloss road marking paint and a preparation method thereof. The method comprises the following steps: adding a high-performance durable emulsion, modified glass microspheres and sodium lauryl sulfate into a stirring kettle for stirring and reacting, cooling the reaction product after the reaction is completed to obtain a durable high-gloss emulsion, and adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener into the durable high-gloss emulsion for stirring and reacting to obtain the durable high-gloss road marking paint. The durable high-gloss road marking paint uses the high-performance durable emulsion as a film-forming substance, imparting good wear resistance and weather resistance to the coating film, and being able to withstand repeated rolling and friction of vehicles as well as erosion by light, oxygen and corrosive media, so that the marking is not easily damaged during long-term use and can maintain the clarity and integrity of the marking for a long time. The modified glass microspheres are added thereto so that the coating film has excellent light-reflecting properties, and the modified glass microspheres are easily and evenly dispersed in the coating, so that the marking can be clearly identified even at night or in a low-light environment, thereby significantly improving the visibility of the marking and enhancing driving safety. Moreover, the preparation method is simple in process and easy to implement industrial production.

[0037] In the process of preparing durable high-gloss road marking paint, a high-performance durable emulsion is first prepared. First, paraformaldehyde and 2,6-di-tert-butylphenol are reacted to introduce hydroxymethyl on the benzene ring of 2,6-di-tert-butylphenol to obtain a hydroxymethyl hindered phenol intermediate. Then, the hydroxymethyl hindered phenol intermediate is reacted with acryloyl chloride. The hydroxymethyl on the hydroxymethyl hindered phenol intermediate reacts with the acyl chloride group on the acryloyl chloride to introduce an olefin group to obtain a hindered phenol polymerization monomer. Finally, methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol The polymerizable monomers are polymerized to obtain a high-performance durable emulsion; the polymer molecular structure of the high-performance durable emulsion contains a large number of hindered phenol structures, which can give it excellent antioxidant properties, prevent the coating from being oxidized and aged by light and oxygen, and prevent the coating from affecting the reflective effect of the coating due to excessive color difference. At the same time, the polymer molecular structure of the high-performance durable emulsion contains a large number of fluorine-containing groups, which give the coating excellent water resistance and corrosion resistance, and improve the lubricity of the coating, and reduce friction loss. Therefore, under the action of the high-performance durable emulsion, the clarity and integrity of the marking can be maintained for a long time, and the durability is greatly improved.

[0038] In the process of preparing durable high-gloss road marking paint, a modified glass microsphere is also prepared. First, the glass microsphere is floated to screen out impurities, solid and broken glass microspheres, thereby improving the uniformity and integrity of the glass microspheres, and thus improving the reflective effect of the coating. The glass microspheres are then pretreated with sodium hydroxide to introduce a large number of hydroxyl groups on their surface, which is convenient for subsequent further modification. Finally, they are modified with γ-mercaptopropyltriethoxysilane. After hydrolysis of γ-mercaptopropyltriethoxysilane, silanol is used to shrink and graft the hydroxyl groups on the surface of the glass microspheres, thereby greatly improving the dispersion performance of the glass microspheres, so that they can be evenly dispersed in the coating, and the introduced mercapto groups can be connected to the polymer molecular structure of the high-performance durable emulsion in the form of chemical bonds through a click chemistry reaction, further improving the compatibility of the two, and improving the interfacial bonding strength of the two, and improving the mechanical properties of the coating. Therefore, under the action of the modified glass microspheres, the road marking can be given excellent reflective properties, thereby improving the visibility of the road marking and improving driving safety. DETAILED DESCRIPTION

[0039] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0040] Example 1:

[0041] This embodiment is a method for preparing a durable high-gloss road marking paint, comprising the following steps:

[0042] Step S1: 2.5 g of paraformaldehyde, 0.13 g of potassium tert-butoxide, and 40 mL of tert-butanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 200 r / min for 30 minutes, and then 30 mmol of 2,6-di-tert-butylphenol was added and the stirring reaction was continued for 4 hours. After the reaction was completed, the reaction product was poured into distilled water, and then the solvent was removed by rotary evaporation, and then recrystallized from n-hexane to obtain a hydroxymethyl hindered phenol intermediate;

[0043] Step S2: 10 mmol of a hydroxymethyl hindered phenol intermediate, 13 mmol of triethylamine, and 40 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was stirred for 10 minutes at a temperature of -5°C and a stirring rate of 200 r / min. Then, 10 mL of a propylene chloride solution prepared by dissolving 11 mmol:10 mL of propylene chloride in dichloromethane was added dropwise while stirring. The dropping rate was controlled to 1 drop / s. After the addition was completed, the mixture was heated to 25°C and the stirring reaction was continued for 7 hours. After the reaction was completed, the reaction product was vacuum filtered, and the filtrate was washed three times with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L, and then dried over anhydrous magnesium sulfate. After vacuum filtration, the filtrate was rotary evaporated to remove the solvent, and then recrystallized with anhydrous ethanol to obtain a hindered phenol polymerization monomer.

[0044] Step S3: 15 g of methyl methacrylate, 15 g of butyl acrylate, 2.3 g of ethylene glycol diacrylate, 5.2 g of lauryl methacrylate, 3.6 g of dodecafluoroheptyl methacrylate, 1.5 g of hindered phenol polymerization monomer, 1.3 g of OP-10 emulsifier, and an AEO-7 emulsifier were mixed in a mass ratio of 2:1 to prepare a composite emulsifier, 0.3 g of sodium bicarbonate, and 50 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was protected by nitrogen and stirred at a temperature of 25° C. and a stirring rate of 200 r / min for 20 min. The mixture was then heated to 85° C. and 10 mL of a 2.5% ammonium persulfate solution was added dropwise while stirring at a rate of 1 drop / s. After the addition was completed, the stirring reaction was continued for 4 h. After the reaction was completed, the reaction product was cooled to room temperature and then passed through a 200-mesh sieve to obtain a high-performance durable emulsion.

[0045] Step S4: 20 g of 3M hollow glass microspheres S28HS and 100 mL of deionized water were added to a beaker, stirred and mixed at a temperature of 25° C. and a stirring rate of 200 r / min for 20 minutes, and then allowed to stand for 2 hours. The upper layer of glass microspheres was collected and placed in a vacuum drying oven and dried at a temperature of 90° C. for 2 hours to obtain flotation glass microspheres;

[0046] Step S5: 10 g of flotation glass microspheres, 1.2 g of sodium hydroxide, and 100 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and stirred at 25° C. and a stirring rate of 200 r / min for 5 minutes, then heated to 45° C. and continued to stir for 4 hours. After the reaction, the reaction product was cooled to room temperature, and then vacuum filtered. The filter cake was washed three times with deionized water and anhydrous ethanol in sequence, and then placed in a vacuum drying oven and dried at 90° C. for 3 hours to obtain pretreated glass microspheres;

[0047] Step S6: 0.5 g of γ-mercaptopropyltriethoxysilane and 100 mL of an 85% volume fraction ethanol solution were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 25° C. and a stirring rate of 200 r / min for 10 minutes. Then, 10 g of pretreated glass microspheres were added and the mixture was heated to 65° C. and the stirring reaction was continued for 4 hours. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed three times with deionized water and anhydrous ethanol in sequence, and then placed in a vacuum drying oven and dried at 70° C. for 2 hours to obtain modified glass microspheres.

[0048] Step S7: Weigh 25 parts of high-performance durable emulsion, 5 parts of modified glass microspheres, 1.1 parts of sodium lauryl sulfate, 0.5 parts of anti-settling and thickening thixotropic agent, 0.2 parts of defoaming agent, 0.2 parts of leveling agent, and 0.1 parts of thickener according to weight, and set aside; the anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is Tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; the thickener is DEURHEO WT-105A thickener;

[0049] Step S8: adding the high-performance durable emulsion, modified glass microspheres, and sodium lauryl sulfate to a stirred kettle, stirring and reacting at a temperature of 25° C. and a stirring rate of 200 r / min for 10 minutes, then heating to 85° C. and continuing stirring and reacting for 3 hours. After the reaction is completed, the reaction product is cooled to room temperature to obtain a durable high-gloss emulsion;

[0050] Step S9: adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener to the durable high-gloss emulsion, stirring and reacting for 30 minutes at a temperature of 25° C. and a stirring rate of 200 r / min to obtain a durable high-gloss road marking paint.

[0051] Example 2:

[0052] This embodiment is a method for preparing a durable high-gloss road marking paint, comprising the following steps:

[0053] Step S1: 2.8 g of paraformaldehyde, 0.15 g of potassium tert-butoxide, and 45 mL of tert-butanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 250 r / min for 32 minutes. Then, 30 mmol of 2,6-di-tert-butylphenol was added and the stirring reaction was continued for 4.5 hours. After the reaction was completed, the reaction product was poured into distilled water, and then the solvent was removed by rotary evaporation. Then, the product was recrystallized from n-hexane to obtain a hydroxymethyl hindered phenol intermediate.

[0054] Step S2: 10 mmol of a hydroxymethyl hindered phenol intermediate, 14 mmol of triethylamine, and 45 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was stirred at -3°C and a stirring rate of 250 r / min for 12 minutes. Then, 10 mL of a propylene chloride solution prepared by dissolving 11 mmol:10 mL of propylene chloride in dichloromethane was added dropwise while stirring. The dropping rate was controlled to 1 drop / s. After the addition was completed, the mixture was heated to 28°C and the stirring reaction was continued for 7.5 hours. After the reaction was completed, the reaction product was vacuum filtered, and the filtrate was washed four times with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L, and then dried over anhydrous magnesium sulfate. The filtrate was vacuum filtered, the solvent was removed by rotary evaporation of the filtrate, and then recrystallized with anhydrous ethanol to obtain a hindered phenol polymerization monomer.

[0055] Step S3: 18 g of methyl methacrylate, 18 g of butyl acrylate, 2.6 g of ethylene glycol diacrylate, 6.4 g of lauryl methacrylate, 5.9 g of dodecafluoroheptyl methacrylate, 3 g of hindered phenol polymerization monomer, 2 g of OP-10 emulsifier, and an AEO-7 emulsifier were mixed in a mass ratio of 2:1 to prepare a composite emulsifier, 0.4 g of sodium bicarbonate, and 52 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was protected by nitrogen and stirred at a temperature of 28° C. and a stirring rate of 250 r / min for 25 minutes. Subsequently, 12 mL of a 2.5% ammonium persulfate solution was added dropwise while heating to 88° C. with stirring at a dropping rate of 1 drop / s. After the addition was completed, the stirring reaction was continued for 4.5 hours. After the reaction was completed, the reaction product was cooled to room temperature and then passed through a 250-mesh sieve to obtain a high-performance durable emulsion.

[0056] Step S4: 20 g of 3M hollow glass microspheres S28HS and 110 mL of deionized water were added to a beaker, stirred and mixed at a temperature of 28° C. and a stirring rate of 250 r / min for 25 minutes, and then allowed to stand for 2.5 hours. The upper layer of glass microspheres was collected and placed in a vacuum drying oven, and dried at a temperature of 95° C. for 2.5 hours to obtain flotation glass microspheres;

[0057] Step S5: 10 g of flotation glass microspheres, 1.4 g of sodium hydroxide, and 105 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and stirred at 28° C. and a stirring rate of 250 r / min for 8 minutes. The mixture was then heated to 48° C. and stirred for 4.5 hours. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed four times with deionized water and anhydrous ethanol in sequence, and then placed in a vacuum drying oven and dried at 95° C. for 3.5 hours to obtain pretreated glass microspheres.

[0058] Step S6: 2.2 g of γ-mercaptopropyltriethoxysilane and 110 mL of an 88% volume fraction ethanol solution were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 28° C. and a stirring rate of 250 r / min for 12 minutes. Subsequently, 10 g of pretreated glass microspheres were added and the mixture was heated to 68° C. and the stirring reaction was continued for 4.5 hours. After the reaction was completed, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed four times with deionized water and anhydrous ethanol in sequence, and then placed in a vacuum drying oven and dried at 72° C. for 2.5 hours to obtain modified glass microspheres.

[0059] Step S7: Weigh 28 parts of high-performance durable emulsion, 9 parts of modified glass microspheres, 1.3 parts of sodium lauryl sulfate, 0.6 parts of anti-settling and thickening thixotropic agent, 0.4 parts of defoaming agent, 0.4 parts of leveling agent, and 0.2 parts of thickener according to weight, and set aside; the anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is Tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; the thickener is DEURHEO WT-105A thickener;

[0060] Step S8: adding the high-performance durable emulsion, modified glass microspheres, and sodium lauryl sulfate to a stirred kettle, stirring and reacting at a temperature of 28° C. and a stirring rate of 250 r / min for 12 minutes, then heating to 88° C. and continuing stirring and reacting for 4 hours. After the reaction is completed, the reaction product is cooled to room temperature to obtain a durable high-gloss emulsion;

[0061] Step S9: adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener to the durable high-gloss emulsion, stirring and reacting for 40 minutes at a temperature of 28° C. and a stirring rate of 250 r / min to obtain a durable high-gloss road marking paint.

[0062] Example 3:

[0063] This embodiment is a method for preparing a durable high-gloss road marking paint, comprising the following steps:

[0064] Step S1: 3.1 g of paraformaldehyde, 0.17 g of potassium tert-butoxide, and 50 mL of tert-butanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 35 minutes, and then 30 mmol of 2,6-di-tert-butylphenol was added and the stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was poured into distilled water, and then the solvent was removed by rotary evaporation, and then recrystallized from n-hexane to obtain a hydroxymethyl hindered phenol intermediate;

[0065] Step S2: 10 mmol of a hydroxymethyl hindered phenol intermediate, 15 mmol of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was stirred at 0° C. and a stirring rate of 300 r / min for 15 minutes. Then, 10 mL of acryloyl chloride was added dropwise while stirring. The acryloyl chloride solution formed by dissolving 12 mmol:10 mL of acryloyl chloride in dichloromethane was added dropwise with stirring. The dropping rate was controlled to 2 drops / s. After the addition was completed, the temperature was raised to 30° C. and the stirring reaction was continued for 8 hours. After the reaction was completed, the reaction product was vacuum filtered, and the filtrate was washed 5 times with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L, and then dried with anhydrous magnesium sulfate. After vacuum filtration, the filtrate was rotary evaporated to remove the solvent, and then recrystallized with anhydrous ethanol to obtain a hindered phenol polymerization monomer;

[0066] Step S3: 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluoroheptyl methacrylate, 4.5 g of hindered phenol polymerization monomer, 2.7 g of OP-10 emulsifier, and AEO-7 emulsifier were mixed in a mass ratio of 2:1 to prepare a composite emulsifier, 0.5 g of sodium bicarbonate, and 55 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was protected by nitrogen and stirred at a temperature of 30° C. and a stirring rate of 300 r / min for 30 min. Subsequently, 15 mL of a 2.5% ammonium persulfate solution was added dropwise while heating to 90° C. with stirring at a dropping rate of 2 drops / s. After the addition was completed, the stirring reaction was continued for 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then passed through a 300-mesh sieve to obtain a high-performance durable emulsion.

[0067] Step S4: 20 g of 3M hollow glass microspheres S28HS and 120 mL of deionized water were added to a beaker, stirred and mixed at a temperature of 30° C. and a stirring rate of 300 r / min for 30 minutes, and then allowed to stand for 3 hours. The upper layer of glass microspheres was collected and placed in a vacuum drying oven and dried at a temperature of 100° C. for 3 hours to obtain flotation glass microspheres;

[0068] Step S5: 10 g of flotation glass microspheres, 1.5 g of sodium hydroxide, and 110 mL of deionized water were added to a three-necked flask equipped with a stirrer and a thermometer, and stirred for reaction at a temperature of 30° C. and a stirring rate of 300 r / min for 10 minutes, then heated to 50° C. and continued to stir for 5 hours. After the reaction, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed with deionized water and anhydrous ethanol five times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 100° C. for 4 hours to obtain pretreated glass microspheres;

[0069] Step S6: 3.9 g of γ-mercaptopropyltriethoxysilane and 120 mL of a 90% volume fraction ethanol solution were added to a three-necked flask equipped with a stirrer and a thermometer, and the mixture was stirred at 30° C. and a stirring rate of 300 r / min for 15 minutes. Then, 10 g of pretreated glass microspheres were added and the mixture was heated to 70° C. and stirred for 5 hours. After the reaction, the reaction product was cooled to room temperature and then vacuum filtered. The filter cake was washed five times with deionized water and anhydrous ethanol in sequence, and then placed in a vacuum drying oven and dried at 75° C. for 3 hours to obtain modified glass microspheres.

[0070] Step S7: 30 parts of high-performance durable emulsion, 13 parts of modified glass microspheres, 1.5 parts of sodium lauryl sulfate, 0.7 parts of anti-settling and thickening thixotropic agent, 0.6 parts of defoaming agent, 0.6 parts of leveling agent, and 0.3 parts of thickener are weighed and set aside; the anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is Tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; and the thickener is DEURHEO WT-105A thickener;

[0071] Step S8: adding the high-performance durable emulsion, modified glass microspheres, and sodium lauryl sulfate to a stirred kettle, stirring and reacting at a temperature of 30° C. and a stirring rate of 300 r / min for 15 minutes, then heating to 90° C. and continuing stirring and reacting for 5 hours. After the reaction is completed, the reaction product is cooled to room temperature to obtain a durable high-gloss emulsion;

[0072] Step S9: adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener to the durable high-gloss emulsion, stirring and reacting for 50 minutes at a temperature of 30° C. and a stirring rate of 300 r / min to obtain a durable high-gloss road marking paint.

[0073] Comparative Example 1:

[0074] This comparative example is a method for preparing a durable high-gloss road marking paint, comprising the following steps:

[0075] Step S1: adding 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 2.7 g of OP-10 emulsifier, and AEO-7 emulsifier in a mass ratio of 2:1 to a composite emulsifier, 0.5 g of sodium bicarbonate, and 55 mL of deionized water to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel, introducing nitrogen protection, stirring and reacting at a temperature of 30° C. and a stirring rate of 300 r / min for 30 minutes, then heating to 90° C. and adding 15 mL of a 2.5% ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 2 drops / s, and continuing to stir and react for 5 hours after the addition is completed. After the reaction is completed, the reaction product is cooled to room temperature and then passed through a 300-mesh sieve to obtain a high-performance durable emulsion;

[0076] Step S2: 30 parts of high-performance durable emulsion, 13 parts of 3M hollow glass microspheres S28HS, 1.5 parts of sodium lauryl sulfate, 0.7 parts of anti-settling and thickening thixotropic agent, 0.6 parts of defoaming agent, 0.6 parts of leveling agent, and 0.3 parts of thickener are weighed and set aside; the anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is Tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; and the thickener is DEURHEO WT-105A thickener;

[0077] Step S3: adding the high-performance durable emulsion, 3M hollow glass microspheres S28HS, and sodium lauryl sulfate to a stirred kettle, stirring the mixture at 30° C. and 300 rpm for 15 minutes, then heating the mixture to 90° C. and continuing stirring the mixture for 5 hours. After the reaction is complete, the reaction product is cooled to room temperature to obtain a durable, high-gloss emulsion.

[0078] Step S4: adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener to the durable high-gloss emulsion, stirring and reacting for 50 minutes at a temperature of 30° C. and a stirring rate of 300 r / min to obtain a durable high-gloss road marking paint.

[0079] Comparative Example 2:

[0080] This comparative example is a method for preparing a durable high-gloss road marking paint, comprising the following steps:

[0081] Step S1: adding 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluoroheptyl methacrylate, 2.7 g of OP-10 emulsifier, and AEO-7 emulsifier in a mass ratio of 2:1 to a composite emulsifier, 0.5 g of sodium bicarbonate, and 55 mL of deionized water to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel, introducing nitrogen protection, stirring and reacting at a temperature of 30° C. and a stirring rate of 300 r / min for 30 minutes, then heating to 90° C. and adding 15 mL of a 2.5% ammonium persulfate solution dropwise while stirring, controlling the dropping rate to 2 drops / s, and continuing to stir and react for 5 hours after the addition is completed. After the reaction is completed, the reaction product is cooled to room temperature and then passed through a 300-mesh sieve to obtain a high-performance durable emulsion;

[0082] Step S2: 30 parts of high-performance durable emulsion, 13 parts of 3M hollow glass microspheres S28HS, 1.5 parts of sodium lauryl sulfate, 0.7 parts of anti-settling and thickening thixotropic agent, 0.6 parts of defoaming agent, 0.6 parts of leveling agent, and 0.3 parts of thickener are weighed and set aside; the anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is Tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; and the thickener is DEURHEO WT-105A thickener;

[0083] Step S3: adding the high-performance durable emulsion, 3M hollow glass microspheres S28HS, and sodium lauryl sulfate to a stirred kettle, stirring the mixture at 30° C. and 300 rpm for 15 minutes, then heating the mixture to 90° C. and continuing stirring the mixture for 5 hours. After the reaction is complete, the reaction product is cooled to room temperature to obtain a durable, high-gloss emulsion.

[0084] Step S4: adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener to the durable high-gloss emulsion, stirring and reacting for 50 minutes at a temperature of 30° C. and a stirring rate of 300 r / min to obtain a durable high-gloss road marking paint.

[0085] Comparative Example 3:

[0086] This comparative example is a method for preparing a durable high-gloss road marking paint, comprising the following steps:

[0087] Step S1: 3.1 g of paraformaldehyde, 0.17 g of potassium tert-butoxide, and 50 mL of tert-butanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 35 minutes, and then 30 mmol of 2,6-di-tert-butylphenol was added and the stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was poured into distilled water, and then the solvent was removed by rotary evaporation, and then recrystallized from n-hexane to obtain a hydroxymethyl hindered phenol intermediate;

[0088] Step S2: 10 mmol of a hydroxymethyl hindered phenol intermediate, 15 mmol of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was stirred at 0° C. and a stirring rate of 300 r / min for 15 minutes. Then, 10 mL of acryloyl chloride was added dropwise while stirring. The acryloyl chloride solution formed by dissolving 12 mmol:10 mL of acryloyl chloride in dichloromethane was added dropwise with stirring. The dropping rate was controlled to 2 drops / s. After the addition was completed, the temperature was raised to 30° C. and the stirring reaction was continued for 8 hours. After the reaction was completed, the reaction product was vacuum filtered, and the filtrate was washed 5 times with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L, and then dried with anhydrous magnesium sulfate. After vacuum filtration, the filtrate was rotary evaporated to remove the solvent, and then recrystallized with anhydrous ethanol to obtain a hindered phenol polymerization monomer;

[0089] Step S3: 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluoroheptyl methacrylate, 4.5 g of hindered phenol polymerization monomer, 2.7 g of OP-10 emulsifier, and AEO-7 emulsifier were mixed in a mass ratio of 2:1 to prepare a composite emulsifier, 0.5 g of sodium bicarbonate, and 55 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was protected by nitrogen and stirred at a temperature of 30° C. and a stirring rate of 300 r / min for 30 min. Subsequently, 15 mL of a 2.5% ammonium persulfate solution was added dropwise while heating to 90° C. with stirring at a dropping rate of 2 drops / s. After the addition was completed, the stirring reaction was continued for 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then passed through a 300-mesh sieve to obtain a high-performance durable emulsion.

[0090] Step S4: 30 parts of high-performance durable emulsion, 13 parts of 3M hollow glass microspheres S28HS, 1.5 parts of sodium lauryl sulfate, 0.7 parts of anti-settling and thickening thixotropic agent, 0.6 parts of defoaming agent, 0.6 parts of leveling agent, and 0.3 parts of thickener are weighed and set aside; the anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is Tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; and the thickener is DEURHEO WT-105A thickener;

[0091] Step S5: adding the high-performance durable emulsion, 3M hollow glass microspheres S28HS, and sodium lauryl sulfate to a stirred kettle, stirring the mixture at 30° C. and 300 rpm for 15 minutes, then heating the mixture to 90° C. and continuing stirring the mixture for 5 hours. After the reaction is complete, the reaction product is cooled to room temperature to obtain a durable, high-gloss emulsion.

[0092] Step S6: adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener to the durable high-gloss emulsion, stirring and reacting for 50 minutes at a temperature of 30° C. and a stirring rate of 300 r / min to obtain a durable high-gloss road marking paint.

[0093] Comparative Example 4:

[0094] This comparative example is a method for preparing a durable high-gloss road marking paint, comprising the following steps:

[0095] Step S1: 3.1 g of paraformaldehyde, 0.17 g of potassium tert-butoxide, and 50 mL of tert-butanol were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 300 r / min for 35 minutes, and then 30 mmol of 2,6-di-tert-butylphenol was added and the stirring reaction was continued for 5 hours. After the reaction was completed, the reaction product was poured into distilled water, and then the solvent was removed by rotary evaporation, and then recrystallized from n-hexane to obtain a hydroxymethyl hindered phenol intermediate;

[0096] Step S2: 10 mmol of a hydroxymethyl hindered phenol intermediate, 15 mmol of triethylamine, and 50 mL of dichloromethane were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was stirred at 0° C. and a stirring rate of 300 r / min for 15 minutes. Then, 10 mL of acryloyl chloride was added dropwise while stirring. The acryloyl chloride solution formed by dissolving 12 mmol:10 mL of acryloyl chloride in dichloromethane was added dropwise with stirring. The dropping rate was controlled to 2 drops / s. After the addition was completed, the temperature was raised to 30° C. and the stirring reaction was continued for 8 hours. After the reaction was completed, the reaction product was vacuum filtered, and the filtrate was washed 5 times with distilled water, a hydrochloric acid solution with a molar concentration of 1 mol / L, and a sodium bicarbonate solution with a molar concentration of 1 mol / L, and then dried with anhydrous magnesium sulfate. After vacuum filtration, the filtrate was rotary evaporated to remove the solvent, and then recrystallized with anhydrous ethanol to obtain a hindered phenol polymerization monomer;

[0097] Step S3: 20 g of methyl methacrylate, 20 g of butyl acrylate, 2.9 g of ethylene glycol diacrylate, 7.6 g of lauryl methacrylate, 8.2 g of dodecafluoroheptyl methacrylate, 4.5 g of hindered phenol polymerization monomer, 2.7 g of OP-10 emulsifier, and AEO-7 emulsifier were mixed in a mass ratio of 2:1 to prepare a composite emulsifier, 0.5 g of sodium bicarbonate, and 55 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube, and a constant pressure dropping funnel. The mixture was protected by nitrogen and stirred at a temperature of 30° C. and a stirring rate of 300 r / min for 30 min. Subsequently, 15 mL of a 2.5% ammonium persulfate solution was added dropwise while heating to 90° C. with stirring at a dropping rate of 2 drops / s. After the addition was completed, the stirring reaction was continued for 5 h. After the reaction was completed, the reaction product was cooled to room temperature and then passed through a 300-mesh sieve to obtain a high-performance durable emulsion.

[0098] Step S4: 20 g of 3M hollow glass microspheres S28HS and 120 mL of deionized water were added to a beaker, stirred and mixed at a temperature of 30° C. and a stirring rate of 300 r / min for 30 minutes, and then allowed to stand for 3 hours. The upper layer of glass microspheres was collected and placed in a vacuum drying oven and dried at a temperature of 100° C. for 3 hours to obtain flotation glass microspheres;

[0099] Step S5: 30 parts of high-performance durable emulsion, 13 parts of flotation glass microspheres, 1.5 parts of sodium lauryl sulfate, 0.7 parts of anti-settling and thickening thixotropic agent, 0.6 parts of defoaming agent, 0.6 parts of leveling agent, and 0.3 parts of thickener are weighed and set aside; the anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is Tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; and the thickener is DEURHEO WT-105A thickener;

[0100] Step S6: adding the high-performance durable emulsion, flotation glass microspheres, and sodium lauryl sulfate to a stirred tank, stirring the mixture at 30° C. and a stirring rate of 300 rpm for 15 minutes, then heating the mixture to 90° C. and continuing stirring the mixture for 5 hours. After the reaction is complete, the reaction product is cooled to room temperature to obtain a durable, high-gloss emulsion.

[0101] Step S7: adding an anti-settling thickening thixotropic agent, a defoaming agent, a leveling agent and a thickener to the durable high-gloss emulsion, stirring and reacting for 50 minutes at a temperature of 30° C. and a stirring rate of 300 r / min to obtain a durable high-gloss road marking paint.

[0102] The durable high-gloss road marking paints of Examples 1-3 and Comparative Examples 1-4 were sprayed onto the tinplate surface and cured to form a coating film with a thickness of 50±2 μm. The coating film properties were then tested. The test results are shown in the following table:

[0103] sample Pencil hardness Water resistance (7d) Chromatic Aberration Example 1 3H No blistering, wrinkling, cracking or peeling 0.86 Example 2 3H No blistering, wrinkling, cracking or peeling 0.81 Example 3 3H No blistering, wrinkling, cracking or peeling 0.77 Comparative Example 1 H There are blistering, wrinkling, and cracking phenomena, but no peeling phenomenon 3.81 Comparative Example 2 H There are blistering, wrinkling, and cracking phenomena, but no peeling phenomenon 1.56 Comparative Example 3 2H There is bubbling, but no wrinkling, cracking or peeling 1.29 Comparative Example 4 3H No blistering, wrinkling, cracking or peeling 1.02

[0104] Among them, the pencil hardness of the sample is tested according to GB / T 6739-2022; the water resistance (7d) of the sample is tested according to GB / T 5209-1985; and the color difference of the sample after 1000h of UV aging is tested according to GB / T 1865-2009.

[0105] Referring to the data in the above table, based on the comparison between Examples 1-3 and Comparative Examples 1-4, it can be seen that the durable high-gloss road marking paint of the present application has excellent water resistance and color difference retention performance.

[0106] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0107] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the scope of protection of the present invention.

Claims

1. A durable high-gloss road marking paint, characterized in that: It comprises the following components in parts by weight: 25-30 parts of high-performance durable emulsion, 5-13 parts of modified glass microspheres, 1.1-1.5 parts of sodium lauryl sulfate, 0.5-0.7 parts of anti-settling and thickening thixotropic agent, 0.2-0.6 parts of defoaming agent, 0.2-0.6 parts of leveling agent and 0.1-0.3 parts of thickener; Wherein, the high performance durable emulsion is prepared by the following steps: Step a1: paraformaldehyde, potassium tert-butoxide, and tert-butanol are stirred for reaction, and then 2,6-di-tert-butylphenol is added and the reaction is continued with stirring. After the reaction is completed, the reaction product is poured into distilled water, and then rotary evaporated and recrystallized to obtain a hydroxymethyl hindered phenol intermediate; Step a2: stirring a hydroxymethyl hindered phenol intermediate, triethylamine, and dichloromethane to react, then adding acryloyl chloride solution dropwise while stirring, continuing to stir and react after the addition is complete, vacuum filtering the reaction product, washing and drying the filtrate, vacuum filtering, rotary evaporating the filtrate, and then recrystallizing to obtain a hindered phenol polymerization monomer; Step a3: stirring and reacting methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol polymerization monomer, composite emulsifier, sodium bicarbonate, and deionized water, then adding ammonium persulfate solution dropwise while stirring, and continuing to stir and react after the addition is complete. After the reaction is completed, the reaction product is cooled and then sieved to obtain a high-performance durable emulsion; The modified glass microspheres are prepared by the following steps: Step b1: stirring and mixing the glass microspheres and deionized water, then allowing the mixture to stand, collecting the upper layer of glass microspheres and drying them to obtain flotation glass microspheres; Step b2: stirring the flotation glass microspheres, sodium hydroxide, and deionized water to react, cooling the reaction product after the reaction is completed, and then vacuum filtering, washing and drying the filter cake to obtain pretreated glass microspheres; Step b3: Stirring the γ-mercaptopropyltriethoxysilane and ethanol solution for reaction, then adding the pretreated glass microspheres and continuing the stirring reaction. After the reaction is completed, the reaction product is cooled, then vacuum filtered, and the filter cake is washed and dried to obtain modified glass microspheres.

2. The durable high-gloss road marking paint according to claim 1, characterized in that: The usage ratio of the paraformaldehyde, potassium tert-butoxide, tert-butanol and 2,6-di-tert-butylphenol in step a1 is 2.5-3.1 g: 0.13-0.17 g: 40-50 mL: 30 mmol.

3. The durable high-gloss road marking paint according to claim 1, characterized in that: The usage ratio of the hydroxymethyl hindered phenol intermediate, triethylamine, dichloromethane and acryloyl chloride solution in step a2 is 10 mmol: 13-15 mmol: 40-50 mL: 10 mL; the acryloyl chloride solution is a solution formed by dissolving acryloyl chloride in dichloromethane at a ratio of 11-12 mmol: 10 mL.

4. The durable high-gloss road marking paint according to claim 1, characterized in that: The amount ratio of the methyl methacrylate, butyl acrylate, ethylene glycol diacrylate, lauryl methacrylate, dodecafluoroheptyl methacrylate, hindered phenol polymerization monomer, composite emulsifier, sodium bicarbonate, deionized water and ammonium persulfate solution in step a3 is 15-20g:15-20g:2.3-2.9g:5.2-7.6g:3.6-8.2g:1.5-4.5g:1.3-2.7g:0.3-0.5g:50-55mL:10-15mL; the mass fraction of the ammonium persulfate solution is 2.5%; the composite emulsifier is a mixture of OP-10 emulsifier and AEO-7 emulsifier in a mass ratio of 2:

1.

5. The durable high-gloss road marking paint according to claim 1, characterized in that: The ratio of the glass microspheres to deionized water in step b1 is 20 g:100-120 mL; the glass microspheres are 3M hollow glass microspheres S28HS.

6. The durable high-gloss road marking paint according to claim 1, characterized in that: The usage ratio of the flotation glass microspheres, sodium hydroxide and deionized water in step b2 is 10 g:1.2-1.5 g:100-110 mL.

7. The durable high-gloss road marking paint according to claim 1, characterized in that: The usage ratio of the γ-mercaptopropyltriethoxysilane, ethanol solution and pretreated glass microspheres in step b3 is 0.5-3.9 g:100-120 mL:10 g; the volume fraction of the ethanol solution is 85-90%.

8. A method for preparing a durable high-gloss road marking paint according to any one of claims 1 to 7, characterized in that: The following steps are involved: Step 1: Weigh 25-30 parts of high-performance durable emulsion, 5-13 parts of modified glass microspheres, 1.1-1.5 parts of sodium lauryl sulfate, 0.5-0.7 parts of anti-settling thickening thixotropic agent, 0.2-0.6 parts of defoaming agent, 0.2-0.6 parts of leveling agent and 0.1-0.3 parts of thickener according to weight parts, and set aside; Step 2: Add the high-performance durable emulsion, modified glass microspheres and sodium lauryl sulfate to a stirred tank, stir and react for 10-15 minutes at a temperature of 25-30°C and a stirring rate of 200-300 r / min, then raise the temperature to 85-90°C and continue stirring and reacting for 3-5 hours. After the reaction is completed, cool the reaction product to room temperature to obtain a durable high-gloss emulsion; Step 3: Add the anti-settling thickening thixotropic agent, defoaming agent, leveling agent and thickener to the durable high-gloss emulsion, stir and react for 30-50 minutes at a temperature of 25-30°C and a stirring rate of 200-300r / min to obtain a durable high-gloss marking paint.

9. The method for preparing a durable high-gloss road marking paint according to claim 8, characterized in that: The anti-settling and thickening thixotropic agent is polyamide wax slurry 4310-20X solvent-based coating anti-settling and thickening thixotropic agent; the defoaming agent is tego810 water-based defoaming agent; the leveling agent is water-based leveling agent BYK-333; and the thickener is DEURHEO WT-105A thickener.