Environment-friendly road sign water-based composite coating and preparation method thereof

Abstract

The invention discloses an environment-friendly road sign water-based composite coating and a preparation method thereof, and relates to the technical field of coatings. The environment-friendly road sign water-based composite coating is prepared from nano MOS2 aqueous dispersion modified water-based acrylic resin, pigment coated combined integrated filler, a 902W defoaming agent, a 4100 wetting agent, a BYK333 flatting agent, propylene glycol phenyl ether and water. Water-based acrylic resin is modified by nano MOS2 aqueous dispersion, and pigment-coated combined integrated filler is added into the formed nano MOS2 aqueous dispersion modified water-based acrylic resin, so that the agglomeration problem caused by separate use of pigment and filler is reduced, the dispersion compatibility and binding property of components in the paint are improved, and the water-based paint has the advantages that the water-based paint can be applied to water-based paint; the drying time is effectively shortened, the wear resistance, the water resistance and the aging resistance of the coating are remarkably improved, and the use durability of the environment-friendly road sign water-based composite coating is prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and specifically refers to an environmentally friendly water-based composite coating for road markings and a preparation method thereof. Background Art

[0002] With the rapid development of road construction in my country, road markings, as important ancillary facilities of highways, play an increasingly significant role in guiding traffic and ensuring driving safety. Therefore, their volume has also increased, and the requirements for road markings have become increasingly higher. Road marking paints are divided into four categories: solvent-based, hot-melt, two-component and water-based road markings. Among them, hot-melt markings have problems such as high volatile organic compounds (VOC) volatilization, difficulty in removing old lines, and high energy consumption in construction. Although two-component road marking paints can adjust the drying time by adjusting the amount of curing agent, it will cause environmental pollution and adverse physical reactions to construction workers. Solvent-based road marking paints can also cause harm to the environment and personnel, and have a long drying time and poor wear resistance, and are not suitable for roads with heavy traffic.

[0003] In recent years, water-based road marking paint has significant advantages such as environmental protection, safety, and easy construction, which has promoted its widespread application in engineering. The main feature of water-based road marking paint is that water is used instead of organic solvents as the dispersant of the resin, and water-based emulsion is used instead of solvent-based resin. Therefore, the volatile organic compound (VOC) content of this type of marking paint is extremely low, and it is an environmentally friendly product.

[0004] The existing technology currently has the following problems:

[0005] Water-based road marking paint takes a long time to dry, which limits the construction period and traffic efficiency. Its low strength and hardness result in poor wear resistance. In addition, due to its insufficient water resistance, it is prone to peeling and blurring when soaked in rainwater, which is not conducive to the durability and safe use of the paint. Summary of the invention

[0006] In view of the above situation, in order to overcome the defects of the prior art, the present invention proposes an environmentally friendly water-based composite coating for road signs, comprising the following components in parts by weight: 60-80 parts of water-based acrylic resin modified by nano-MOS2 aqueous dispersion, 30-50 parts of pigment-coated combined integrated filler, 3-5 parts of 902W defoamer, 5-8 parts of 4100 wetting agent, 5-8 parts of BYK333 leveling agent, 3-5 parts of propylene glycol phenyl ether, and 10-20 parts of water.

[0007] The pigment-coated combined integrated filler comprises the following components in parts by weight: 5-8 parts of graphene oxide metal organic framework composite material, 8-10 parts of titanium dioxide, and 8-10 parts of calcium carbonate powder.

[0008] The nano-MOS2 water dispersion modified water-based acrylic resin comprises the following components in parts by weight: 15-25 parts of nano-MOS2 water dispersion and 70-80 parts of water-based acrylic resin.

[0009] The method for preparing the pigment-coated combined integrated filler specifically comprises the following steps:

[0010] (1) 0.1-0.3 g of graphene oxide powder was washed with methanol for 3-5 times and then added to 20 mL of methanol solution. Anhydrous cobalt acetate solid was then added to the methanol solution containing graphene oxide, stirred thoroughly and set aside. Then 2.0 g of 2-methylimidazole was dissolved in 20 mL of methanol solution and then dropped into the methanol solution containing graphene oxide and anhydrous cobalt acetate to achieve the growth of metal organic framework ZIF-67 nanoparticles on the surface of graphene oxide sheets. The mixture was stirred at 100-200 rpm for 20-30 min, allowed to stand for 24 h, centrifuged, and the precipitate was washed with methanol solution for 3 min. -5 times, vacuum drying, through this process, a composite material of graphene oxide and ZIF-67 is generated, which not only reduces the aggregation of graphene oxide nanosheets, improves the dispersibility and compatibility of the composite material in the water-based acrylic resin matrix, but also can play the role of ZIF-67 as a curing agent, can react with the functional groups in the water-based acrylic resin to form a cross-linked structure, accelerate the curing process of the resin, and help to improve the hardness, heat resistance and water resistance of the water-based acrylic resin, can better resist the adverse effects of wear, aging and rain, improve durability, and obtain a graphene oxide metal organic framework composite material;

[0011] (2) Dissolve 8.0-10.0 g of titanium dioxide and 20-30 mL of KH560 in 100 mL of methanol solution, and heat the reaction at 40-45° C. for 12 h at constant temperature and condensation reflux. Set aside. Disperse the graphene oxide metal organic framework composite material described in step (1) in 20 mL of deionized water. Add the methanol solution containing titanium dioxide and KH560. React at room temperature for 10-12 h. Dry in an oven. The addition of graphene oxide and metal organic framework composite material improves the dispersibility and fluidity of titanium dioxide, and can obtain a better coating effect, thereby obtaining a composite filler of graphene oxide metal organic framework composite material and titanium dioxide.

[0012] (3) Add 200 mL of 4% sodium hydroxide solution and 8.0-10.0 g of calcium carbonate powder into a three-necked flask, stir at 60-70°C for 0.5-1 h, wash with water until neutral and filter, vacuum dry the pretreated calcium carbonate, and set aside the alkali-washed calcium carbonate powder. Prepare 200 mL of ethanol aqueous solution containing KH560, add the alkali-washed calcium carbonate powder, stir at 60-70°C for 1-2 h, filter and wash with anhydrous ethanol for 3-5 times, and vacuum dry the filter cake to obtain KH560 modified alkali-washed calcium carbonate powder. Then add the graphene oxide metal organic framework composite material and titanium dioxide composite material ... The suspension is filtered, washed with water for 3-5 times, and vacuum dried, and the combined filler of graphene oxide metal organic framework composite material and titanium dioxide is dispersed in an aqueous medium, and then adsorbed onto the surface of KH560 modified alkali-washed calcium carbonate powder, forming a coating of KH560 modified alkali-washed calcium carbonate powder by the combined filler of graphene oxide metal organic framework composite material and titanium dioxide. The prepared integrated composite material of pigment and filler can reduce the agglomeration phenomenon caused by differences in density, particle size and surface properties, improve the uniform dispersibility of the composite material in water-based acrylic resin, and give full play to the maximized role of titanium dioxide, calcium carbonate powder and graphene oxide metal organic framework composite material as combined filler, improve the crosslinking density with resin in multiple dimensions, help improve wear resistance, water resistance and aging resistance, and obtain pigment-coated combined integrated filler;

[0013] Preferably, in step (1), the amount of anhydrous cobalt acetate added is 1.0-2.0 g. Cobalt ions act as catalysts to increase the crosslinking density and curing time of the resin, which can not only shorten the construction period but also ensure the quality and durability of the coating after curing.

[0014] Preferably, in step (3), in the ethanol aqueous solution containing KH560, the volume ratio of KH560, water and anhydrous ethanol is 1:3:6. The modification treatment of KH560 further enhances the dispersibility of the alkali-washed calcium carbonate powder in the organic medium, which is conducive to a better subsequent coating effect.

[0015] The present invention also provides a method for preparing an environmentally friendly road sign water-based composite coating, which specifically comprises the following steps:

[0016] S1, the MOS2 powder is mechanically ball-milled by a high-speed vibration ball mill, and then the treated MOS2 powder is added to 200mL of deionized water containing 0.04g of sodium dodecyl sulfate, and then ultrasonicated by an ultrasonic cleaning machine for 1-2h. After standing for 8-10h, the well-dispersed solution on the upper layer is collected and placed in an oven for drying. The powder after sieving is smaller in particle size and more evenly distributed. The obtained nano-MOS2 powder after sieving is added to 200mL of deionized water containing 0.04g of sodium dodecyl sulfate, fully stirred, and then ultrasonicated by an ultrasonic cell crusher for 5-10min, which further ensures the excellent dispersibility and stability of nano-MOS2 in water-based acrylic resin, and is conducive to the improvement of the wear resistance, adhesion, durability and anti-aging properties of the resin by nano-MOS2, and obtains a nano-MOS2 aqueous dispersion;

[0017] S2, adding the nano-MOS2 aqueous dispersion described in step S1 into a three-necked flask, heating to 110-130°C, weighing 8.0g acrylic acid, 20.0g butyl methacrylate, 30.0-40.0g methyl methacrylate, 12.0g hydroxypropyl acrylate, 0.5g tert-butyl perbenzoate, and 3.0g 2,4-diphenyl-4-methyl-1-pentene, respectively, mixing evenly, and then dropping into the three-necked flask, the dropping time is 2-3h, and the reaction is kept warm for 0.5-1h, and then cooled to 80°C, 0.5g N,N-dimethylethanolamine is added to neutralize for 10-20min, and the water-based acrylic resin is prepared from acrylic monomers. In the process, a nano-MOS2 aqueous dispersion is introduced for modification treatment, wherein the nano-MOS2 has excellent strength and hardness, and can significantly improve the wear resistance of the water-based acrylic resin. The nano-MOS2 also has good chemical stability and weather resistance, and can improve the weather resistance and anti-aging properties of the water-based acrylic resin, so that it can maintain good performance under various climatic conditions. The sulfur atoms in the nano-MOS2 act as a catalyst to accelerate the polymerization reaction of the resin and improve the reaction efficiency. The sulfur atoms also have heat resistance and chemical resistance, etc., which contribute to the stability of the polymerization product, thereby obtaining a water-based acrylic resin modified by a nano-MOS2 aqueous dispersion;

[0018] S3, adding the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion described in step S2 into a blender, stirring at a speed of 400-500rpm for 5-10min, adding 902W defoamer, 4100 wetting agent, BYK333 leveling agent, stirring for 3-5min, and then adding a small amount of pigment-coated combined integrated filler multiple times, adjusting the speed to 800-1000rpm and stirring for 10-20min after adding, then reducing the speed to 600rpm, and then adding propylene glycol phenyl ether and water. Propylene glycol phenyl ether, as a film-forming agent, can reduce the content of volatile organic matter in the coating and give the coating better agglomeration performance. After all the components are added, adjusting the speed to 800-1000rpm and stirring for 10-20min, the pigment-coated combined integrated filler is stirred for 10 minutes. The body filler can be evenly dispersed in the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion, and the catalytic effect can effectively improve the crosslinking density and curing process with the resin, which not only shortens the drying time, but also improves the surface strength and hardness, heat resistance stability through the formed dense structure, and reduces the penetration of water, thereby significantly improving the wear resistance, water resistance and aging resistance, and extending the service life of the coating. Among them, in the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion, the nano-MOS2 can form a good interface with other components in the coating, enhance the adhesion and bonding force of the coating, better resist external wear, rain erosion and high temperature, thereby reducing the occurrence of coating peeling, shedding and cracking, and obtaining an environmentally friendly road sign water-based composite coating;

[0019] Preferably, in step S1, during the mechanical ball milling process, the ball milling speed is 10000-12000 rpm, and the ball milling time is 70-90 min. The MOS2 layer is effectively peeled off by ball milling, thereby increasing the specific surface area and increasing the number of active sites.

[0020] The beneficial effects achieved by the present invention are as follows:

[0021] The invention modifies water-based acrylic resin with nano-MOS2 water dispersion, and then adds pigment-coated combined integrated filler to the formed water-based acrylic resin modified by nano-MOS2 water dispersion, thereby reducing the agglomeration problem caused by separate use of pigment and filler, improving the dispersion compatibility and bonding of various components in the coating, effectively shortening the drying time, significantly improving the wear resistance, water resistance and aging resistance of the coating, and extending the service durability of the environmentally friendly water-based composite coating for road signs; the nano-MOS2 introduced into the water-based acrylic resin modified by the nano-MOS2 water dispersion has excellent strength and hardness, and can also form a good bond with other components in the coating. Good interface bonding, enhances the adhesion and bonding of the coating, reduces the wear, shedding and cracking of the coating, and effectively resists the adverse effects of wear, moisture and high temperature on the coating after curing. Among them, the sulfur atom not only enhances the cross-linking density of the water-based acrylic acid, but also can form a strong chemical bond with the pigment-coated combined integrated filler and other materials, which not only improves the drying rate, but also enhances the density and stability of the coating. The high-temperature strength and anti-friction performance of the molybdenum atom keep it stable in a high-temperature environment, reducing the problem of coating performance degradation caused by high temperature; in the pigment-coated combined integrated filler, titanium dioxide is first dispersed in the graphene oxide metal organic framework composite material Structurally, it is coated on the surface of calcium carbonate powder to form an integrated composite material of pigment and filler, which exhibits excellent dispersion compatibility in the resin matrix, reduces the adverse effects of using pigments and fillers alone on each other's dispersibility, and can also maximize the effects of pigments and fillers in a three-in-one manner. In addition, the metal organic framework ZIF-67 nanoparticles are doped on the surface of graphene oxide sheets, which not only reduces the aggregation of graphene oxide nanosheets and improves the dispersibility of the integrated filler in the water-based acrylic resin matrix, but also can play the catalytic curing role of ZIF-67, promote the cross-linking reaction between the integrated filler and the functional groups in the resin, increase the cross-linking density, and accelerate the curing process. The process helps to improve the hardness, heat resistance and water resistance of the coating, and the compact lamellar structure of graphene oxide can also block the penetration of water. Its excellent high thermal conductivity and high strength characteristics also help to improve the heat resistance and mechanical properties of the coating, further enhancing the durability of the coating. The present invention uses nano-MOS2 water dispersion to modify water-based acrylic resin, pigment-coated combined integrated filler, 902W defoamer, 4100 wetting agent, BYK333 leveling agent, propylene glycol phenyl ether and water to prepare an environmentally friendly road sign water-based composite coating, which not only has a fast drying rate, but also has excellent wear resistance, water resistance and aging resistance, and effectively prolongs the service life of the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a scanning electron microscope image of the environmentally friendly road sign water-based composite coating prepared in Example 1 of the present invention;

[0023] Figure 2 The non-stick tire drying time result diagram of Examples 1-4 of the present invention and Comparative Examples 1-3;

[0024] Figure 3 The figures are the results of wear of Examples 1-4 and Comparative Examples 1-3 of the present invention;

[0025] Figure 4 The water resistance time results of Examples 1-4 and Comparative Examples 1-3 of the present invention are shown in FIG.

[0026] Figure 5 It is a graph showing the aging time results of Examples 1-4 of the present invention and Comparative Examples 1-3. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0028] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.

[0029] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials used in the following examples are purchased from commercial channels unless otherwise specified.

[0030] Example 1

[0031] This embodiment proposes an environmentally friendly water-based composite coating for road signs, comprising the following components in parts by weight: 80 parts of water-based acrylic resin modified by nano-MOS2 aqueous dispersion, 50 parts of pigment-coated combined integrated filler, 5 parts of 902W defoamer, 8 parts of 4100 wetting agent, 8 parts of BYK333 leveling agent, 5 parts of propylene glycol phenyl ether, and 20 parts of water.

[0032] The pigment-coated combined integrated filler comprises the following components in parts by weight: 8 parts of graphene oxide metal organic framework composite material, 10 parts of titanium dioxide, and 10 parts of calcium carbonate powder.

[0033] The nano-MOS2 water dispersion modified water-based acrylic resin comprises the following components in parts by weight: 25 parts of the nano-MOS2 water dispersion and 80 parts of the water-based acrylic resin.

[0034] The preparation method of the pigment-coated combined integrated filler specifically comprises the following steps:

[0035] (1) 0.3 g of graphene oxide powder was washed with methanol for 5 times and then added to 20 mL of methanol solution. Then, anhydrous cobalt acetate solid was added to the methanol solution containing graphene oxide, stirred thoroughly and set aside. The amount of anhydrous cobalt acetate added was 2.0 g. Cobalt ions acted as a catalyst to increase the crosslinking density and curing time of the resin, which not only shortened the construction period but also ensured the quality and durability of the coating after curing. Then, 2.0 g of 2-methylimidazole was dissolved in 20 mL of methanol solution and then dropped into the methanol solution containing graphene oxide and anhydrous cobalt acetate. The growth of metal organic framework ZIF-67 nanoparticles on the surface of graphene oxide sheets was achieved at a speed of 200 rpm. Stirring for 30 minutes, standing for 24 hours, centrifuging, washing the precipitate with methanol solution for 5 times, and vacuum drying, a composite material of graphene oxide and ZIF-67 is generated through this process, which not only reduces the aggregation of graphene oxide nanosheets, improves the dispersibility and compatibility of the composite material in the water-based acrylic resin matrix, but also can play the role of ZIF-67 as a curing agent, can react with the functional groups in the water-based acrylic resin to form a cross-linked structure, accelerate the curing process of the resin, and help to improve the hardness, heat resistance and water resistance of the water-based acrylic resin, can better resist the adverse effects of wear, aging and rain, improve durability, and obtain a graphene oxide metal organic framework composite material;

[0036] (2) Dissolve 10.0 g of titanium dioxide and 30 mL of KH560 in 100 mL of methanol solution, and heat the reaction at 45° C. for 12 h at constant temperature and reflux, and then disperse the graphene oxide metal organic framework composite material described in step (1) in 20 mL of deionized water, and then add the methanol solution containing titanium dioxide and KH560, and react at room temperature for 12 h. The mixture is then dried in an oven. The addition of graphene oxide and the metal organic framework composite material improves the dispersibility and fluidity of titanium dioxide, and a better coating effect can be obtained, thereby obtaining a composite filler of graphene oxide metal organic framework composite material and titanium dioxide.

[0037] (3) Add 200 mL of 4% sodium hydroxide solution and 10.0 g of calcium carbonate powder into a three-necked flask, stir at 70°C for 1 h, wash with water until neutral and filter, vacuum dry the pretreated calcium carbonate, and set aside the alkali-washed calcium carbonate powder. Prepare 200 mL of ethanol aqueous solution containing KH560, add the alkali-washed calcium carbonate powder, and stir at 70°C for 2 h. In the ethanol aqueous solution containing KH560, the volume ratio of KH560, water and anhydrous ethanol is 1:3:6. The modified treatment of KH560 further enhances the dispersibility of the alkali-washed calcium carbonate powder in the organic medium, which is conducive to a better subsequent coating effect. Filter and wash with anhydrous ethanol for 5 times. The filter cake is vacuum dried to obtain KH560 modified alkali-washed calcium carbonate powder. Then, the graphene oxide metal organic framework composite material and titanium dioxide combined filler described in step (2) are added to 150 mL of deionized water, ultrasonicated for 30 min, and KH560 modified alkali is added. The calcium carbonate powder was washed, stirred at 80°C for 2h, and separated by standing with a separatory funnel. The upper suspension was filtered, washed with water for 5 times, and vacuum dried. The combined filler of graphene oxide metal organic framework composite material and titanium dioxide was dispersed in an aqueous medium, and then adsorbed onto the surface of KH560 modified alkali-washed calcium carbonate powder, forming a coating of KH560 modified alkali-washed calcium carbonate powder by the combined filler of graphene oxide metal organic framework composite material and titanium dioxide. The prepared integrated composite material of pigment and filler can reduce the agglomeration phenomenon caused by differences in density, particle size and surface properties, and improve the uniform dispersibility of the composite material in water-based acrylic resin, and give full play to the maximized role of titanium dioxide, calcium carbonate powder and graphene oxide metal organic framework composite material as combined fillers, and improve the crosslinking density with the resin in multiple dimensions, which is helpful to improve wear resistance, water resistance and aging resistance, and obtain a pigment-coated combined integrated filler.

[0038] This embodiment provides a method for preparing an environmentally friendly water-based composite coating for road markings, which specifically comprises the following steps:

[0039] S1. The MOS2 powder is mechanically ball-milled by a high-speed vibration ball mill. During the mechanical ball-milling process, the ball-milling speed is 12000 rpm and the ball-milling time is 90 min. The MOS2 flakes are effectively peeled off by ball-milling treatment, thereby increasing the specific surface area and increasing the number of active sites. The treated MOS2 powder is then added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, and then ultrasonicated for 2 h using an ultrasonic cleaner. After standing for 10 h, the well-dispersed upper solution is collected and placed in an oven for drying. The powder after sieving has a smaller particle size and a more uniform distribution. The obtained nano-MOS2 powder after sieving is added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, fully stirred, and then ultrasonicated for 10 min using an ultrasonic cell crusher, which further ensures the excellent dispersibility and stability of nano-MOS2 in water-based acrylic resin, and is conducive to the improvement of the wear resistance, adhesion, durability and anti-aging properties of the resin by nano-MOS2, thereby obtaining a nano-MOS2 aqueous dispersion.

[0040] S2, adding the nano-MOS2 aqueous dispersion described in step S1 into a three-necked flask, heating to 130°C, weighing 8.0g acrylic acid, 20.0g butyl methacrylate, 40.0g methyl methacrylate, 12.0g hydroxypropyl acrylate, 0.5g tert-butyl perbenzoate, and 3.0g 2,4-diphenyl-4-methyl-1-pentene, respectively, mixing evenly, and then dropping into the three-necked flask, the dropping time is 3h, and the temperature is kept for reaction for 1h, and then cooled to 80°C, 0.5g N,N-dimethylethanolamine is added and neutralized for 20min, and nano-MO is introduced into the process of preparing water-based acrylic resin from acrylic monomers. S2 aqueous dispersion is modified, wherein nano-MOS2 has excellent strength and hardness, can significantly improve the wear resistance of water-based acrylic resin, nano-MOS2 also has good chemical stability and weather resistance, can improve the weather resistance and anti-aging performance of water-based acrylic resin, so that it can maintain good performance under various climatic conditions, and the sulfur atom in nano-MOS2 can accelerate the polymerization reaction of the resin and improve the reaction efficiency as a catalyst, and the sulfur atom also has heat resistance and chemical resistance, etc., which contributes to the stability of the polymerization product, so as to obtain nano-MOS2 aqueous dispersion modified water-based acrylic resin;

[0041] S3, adding the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion described in step S2 into a mixer, stirring at a speed of 500 rpm for 10 min, adding 902W defoamer, 4100 wetting agent, BYK333 leveling agent, stirring for 5 min, and then adding the pigment-coated combined integrated filler in small amounts and multiple times. After adding, adjusting the speed to 1000 rpm and stirring for 20 min, then reducing the speed to 600 rpm, and then adding propylene glycol phenyl ether and water. Propylene glycol phenyl ether is used as a film-forming agent to reduce the content of volatile organic matter in the coating and give the coating better agglomeration performance. After all components are added, adjusting the speed to 1000 rpm and stirring for 20 min, the pigment-coated combined integrated filler is in the nano-MOS2 The water dispersion modified water-based acrylic resin can be evenly dispersed, and the catalytic effect can effectively improve the crosslinking density and curing process with the resin, which not only shortens the drying time, but also improves the surface strength and hardness, heat resistance and stability through the formed dense structure, and reduces the penetration of water, thereby significantly improving the wear resistance, water resistance and aging resistance, and extending the service life of the coating. Among them, in the water-based acrylic resin modified by the nano-MOS2 water dispersion, the nano-MOS2 can form a good interface bonding with other components in the coating, enhance the adhesion and bonding force of the coating, and better resist external wear, rain erosion and high temperature, thereby reducing the occurrence of coating peeling, shedding and cracking, and obtaining an environmentally friendly road sign water-based composite coating.

[0042] In this embodiment, the prepared environmentally friendly road sign water-based composite coating was subjected to a scanning electron microscope to observe its microscopic morphology. Figure 1 This is a SEM image of the environmentally friendly road sign water-based composite coating prepared in Example 1, magnified 5000 times. Figure 1 The environmentally friendly road sign water-based composite coating prepared in this embodiment has good dispersibility and density.

[0043] Example 2

[0044] This embodiment proposes an environmentally friendly water-based composite coating for road signs, comprising the following components in parts by weight: 60 parts of water-based acrylic resin modified by nano-MOS2 aqueous dispersion, 30 parts of pigment-coated combined integrated filler, 3 parts of 902W defoamer, 5 parts of 4100 wetting agent, 5 parts of BYK333 leveling agent, 3 parts of propylene glycol phenyl ether, and 10 parts of water.

[0045] The pigment-coated combined integrated filler comprises the following components in parts by weight: 5 parts of graphene oxide metal organic framework composite material, 8 parts of titanium dioxide, and 8 parts of calcium carbonate powder.

[0046] The nano-MOS2 water dispersion modified water-based acrylic resin comprises the following components in parts by weight: 15 parts of the nano-MOS2 water dispersion and 70 parts of the water-based acrylic resin.

[0047] The preparation method of the pigment-coated combined integrated filler specifically comprises the following steps:

[0048] (1) 0.1 g of graphene oxide powder was washed three times with methanol and then added to 20 mL of methanol solution. Anhydrous cobalt acetate solid was then added to the methanol solution containing graphene oxide, stirred thoroughly and set aside. The amount of anhydrous cobalt acetate added was 1.0 g. Cobalt ions acted as a catalyst to increase the crosslinking density and curing time of the resin, which not only shortened the construction period but also ensured the quality and durability of the coating after curing. Then 2.0 g of 2-methylimidazole was dissolved in 20 mL of methanol solution and then dropped into the methanol solution containing graphene oxide and anhydrous cobalt acetate. The growth of metal organic framework ZIF-67 nanoparticles on the surface of graphene oxide sheets was achieved at a speed of 100 rpm. Stirring for 20 minutes, standing for 24 hours, centrifuging, washing the precipitate with methanol solution for 3 times, and vacuum drying, a composite material of graphene oxide and ZIF-67 is generated through this process, which not only reduces the aggregation of graphene oxide nanosheets, improves the dispersibility and compatibility of the composite material in the water-based acrylic resin matrix, but also can play the role of ZIF-67 as a curing agent, can react with the functional groups in the water-based acrylic resin to form a cross-linked structure, accelerate the curing process of the resin, and help to improve the hardness, heat resistance and water resistance of the water-based acrylic resin, can better resist the adverse effects of wear, aging and rain, improve durability, and obtain a graphene oxide metal organic framework composite material;

[0049] (2) 8.0 g of titanium dioxide and 20 mL of KH560 were dissolved in 100 mL of methanol solution, the reaction temperature was 40° C., and the reaction was carried out under constant temperature condensation reflux for 12 h, and then the graphene oxide metal organic framework composite material described in step (1) was dispersed in 20 mL of deionized water, and then the methanol solution containing titanium dioxide and KH560 was added, and the reaction was carried out at room temperature for 10 h, and then the mixture was dried in an oven. The addition of graphene oxide and the metal organic framework composite material improved the dispersibility and fluidity of titanium dioxide, and a better coating effect was obtained, thereby obtaining a composite filler of graphene oxide metal organic framework composite material and titanium dioxide;

[0050] (3) Add 200 mL of 4% sodium hydroxide solution and 8.0 g of calcium carbonate powder into a three-necked flask, stir at 60°C for 0.5 h, wash with water until neutral and filter, vacuum dry the pretreated calcium carbonate, and set aside the alkali-washed calcium carbonate powder. Prepare 200 mL of ethanol aqueous solution containing KH560, add the alkali-washed calcium carbonate powder, and stir at 60°C for 1 h. In the ethanol aqueous solution containing KH560, the volume ratio of KH560, water and anhydrous ethanol is 1:3:6. The modified treatment of KH560 further enhances the dispersibility of the alkali-washed calcium carbonate powder in the organic medium, which is conducive to a better subsequent coating effect. Filter and wash with anhydrous ethanol for 3 times. The filter cake is vacuum dried to obtain KH560 modified alkali-washed calcium carbonate powder. Then, the graphene oxide metal organic framework composite material and titanium dioxide composite material combined filler described in step (2) are added to 150 mL of deionized water, ultrasonicated for 20 min, and KH560 modified alkali is added. The calcium carbonate powder was washed, stirred at 70°C for 1 hour, and separated by standing with a separatory funnel. The upper suspension was filtered, washed with water for 3 times, and vacuum dried. The combined filler of graphene oxide metal organic framework composite material and titanium dioxide was dispersed in an aqueous medium, and then adsorbed onto the surface of KH560 modified alkali-washed calcium carbonate powder, forming a coating of KH560 modified alkali-washed calcium carbonate powder by the combined filler of graphene oxide metal organic framework composite material and titanium dioxide. The prepared integrated composite material of pigment and filler can reduce the agglomeration phenomenon caused by differences in density, particle size and surface properties, and improve the uniform dispersibility of the composite material in water-based acrylic resin, and give full play to the maximized role of titanium dioxide, calcium carbonate powder and graphene oxide metal organic framework composite material as combined fillers, and improve the crosslinking density with the resin in multiple dimensions, which is helpful to improve wear resistance, water resistance and aging resistance, and obtain a pigment-coated combined integrated filler.

[0051] This embodiment provides a method for preparing an environmentally friendly water-based composite coating for road markings, which specifically comprises the following steps:

[0052] S1. The MOS2 powder is mechanically ball-milled by a high-speed vibration ball mill. During the mechanical ball-milling process, the ball-milling speed is 10000 rpm and the ball-milling time is 70 min. The MOS2 flakes are effectively peeled off by ball-milling treatment, thereby increasing the specific surface area and increasing the number of active sites. The treated MOS2 powder is then added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, and then ultrasonicated for 1 h using an ultrasonic cleaning machine. After standing for 8 h, the well-dispersed upper solution is collected and placed in an oven for drying. The powder particle size after sieving is smaller and the distribution is more uniform. The obtained nano-MOS2 powder after sieving is added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, fully stirred, and then ultrasonicated for 5 min using an ultrasonic cell crusher, which further ensures the excellent dispersibility and stability of nano-MOS2 in water-based acrylic resin, and is conducive to the improvement of the wear resistance, adhesion, durability and anti-aging properties of the resin by nano-MOS2, thereby obtaining a nano-MOS2 aqueous dispersion.

[0053] S2, adding the nano-MOS2 aqueous dispersion described in step S1 into a three-necked flask, heating to 110°C, weighing 8.0g acrylic acid, 20.0g butyl methacrylate, 30.0g methyl methacrylate, 12.0g hydroxypropyl acrylate, 0.5g tert-butyl perbenzoate, and 3.0g 2,4-diphenyl-4-methyl-1-pentene, respectively, mixing evenly, and then dropping into the three-necked flask, the dropping time is 2h, and the temperature is kept for reaction for 0.5h, and then cooled to 80°C, 0.5g N,N-dimethylethanolamine is added and neutralized for 10min, and nano-MOS2 is introduced into the process of preparing water-based acrylic resin from acrylic monomers. OS2 aqueous dispersion is modified, wherein nano-MOS2 has excellent strength and hardness, can significantly improve the wear resistance of water-based acrylic resin, nano-MOS2 also has good chemical stability and weather resistance, can improve the weather resistance and anti-aging performance of water-based acrylic resin, so that it can maintain good performance under various climatic conditions, and the sulfur atom in nano-MOS2 as a catalyst can accelerate the polymerization reaction of the resin and improve the reaction efficiency, the sulfur atom also has heat resistance and chemical resistance, etc., which is conducive to the stability of the polymerization product, and the nano-MOS2 aqueous dispersion modified water-based acrylic resin is obtained;

[0054] S3, adding the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion described in step S2 into a stirrer, stirring at a speed of 400 rpm for 5 min, adding 902W defoamer, 4100 wetting agent, BYK333 leveling agent, stirring for 3 min, and then adding the pigment-coated combined integrated filler in small amounts and multiple times. After adding, adjusting the speed to 800 rpm and stirring for 10 min, then reducing the speed to 600 rpm, and then adding propylene glycol phenyl ether and water. Propylene glycol phenyl ether is used as a film-forming agent to reduce the content of volatile organic matter in the coating and give the coating better agglomeration performance. After all components are added, adjusting the speed to 800 rpm and stirring for 10 min. The pigment-coated combined integrated filler is in the nano-MOS2 water. The dispersion can be evenly dispersed in the modified water-based acrylic resin, and the catalytic effect can effectively improve the crosslinking density and curing process with the resin, which not only shortens the drying time, but also improves the surface strength and hardness, heat resistance and stability through the formed dense structure, and reduces the penetration of water, thereby significantly improving the wear resistance, water resistance and aging resistance, and extending the service life of the coating. Among them, in the water-based acrylic resin modified by the nano-MOS2 water dispersion, the nano-MOS2 can form a good interface bonding with other components in the coating, enhance the adhesion and bonding force of the coating, and better resist external wear, rain erosion and high temperature, thereby reducing the occurrence of coating peeling, shedding and cracking, and obtaining an environmentally friendly road sign water-based composite coating.

[0055] Example 3

[0056] This embodiment proposes an environmentally friendly water-based composite coating for road signs, comprising the following components in parts by weight: 70 parts of water-based acrylic resin modified by nano-MOS2 aqueous dispersion, 40 parts of pigment-coated combined integrated filler, 4 parts of 902W defoamer, 6.5 parts of 4100 wetting agent, 6.5 parts of BYK333 leveling agent, 4 parts of propylene glycol phenyl ether, and 15 parts of water.

[0057] The pigment-coated combined integrated filler comprises the following components in parts by weight: 6.5 parts of graphene oxide metal organic framework composite material, 9 parts of titanium dioxide, and 9 parts of calcium carbonate powder.

[0058] The nano-MOS2 water dispersion modified water-based acrylic resin comprises the following components in parts by weight: 20 parts of the nano-MOS2 water dispersion and 75 parts of the water-based acrylic resin.

[0059] The preparation method of the pigment-coated combined integrated filler specifically comprises the following steps:

[0060] (1) 0.2 g of graphene oxide powder was washed four times with methanol and then added to 20 mL of methanol solution. Anhydrous cobalt acetate solid was then added to the methanol solution containing graphene oxide, stirred thoroughly and set aside. The amount of anhydrous cobalt acetate added was 1.5 g. Cobalt ions acted as a catalyst to increase the crosslinking density and curing time of the resin, which not only shortened the construction period but also ensured the quality and durability of the coating after curing. Then 2.0 g of 2-methylimidazole was dissolved in 20 mL of methanol solution and then dropped into the methanol solution containing graphene oxide and anhydrous cobalt acetate. The growth of metal organic framework ZIF-67 nanoparticles on the surface of graphene oxide sheets was achieved at a speed of 150 rpm. Stirring for 25 minutes, standing for 24 hours, centrifuging, washing the precipitate with methanol solution for 4 times, and vacuum drying, a composite material of graphene oxide and ZIF-67 is generated through this process, which not only reduces the aggregation of graphene oxide nanosheets, improves the dispersibility and compatibility of the composite material in the water-based acrylic resin matrix, but also can play the role of ZIF-67 as a curing agent, can react with the functional groups in the water-based acrylic resin to form a cross-linked structure, accelerate the curing process of the resin, and help to improve the hardness, heat resistance and water resistance of the water-based acrylic resin, can better resist the adverse effects of wear, aging and rain, improve durability, and obtain a graphene oxide metal organic framework composite material;

[0061] (2) 9.0 g of titanium dioxide and 25 mL of KH560 were dissolved in 100 mL of methanol solution, the reaction temperature was 42.5° C., and the reaction was carried out under constant temperature condensation reflux for 12 h, and then the graphene oxide metal organic framework composite material described in step (1) was dispersed in 20 mL of deionized water, and then the methanol solution containing titanium dioxide and KH560 was added, and the reaction was carried out at room temperature for 11 h, and then the mixture was dried in an oven. The addition of graphene oxide and metal organic framework composite material improved the dispersibility and fluidity of titanium dioxide, and a better coating effect was obtained, thereby obtaining a composite filler of graphene oxide metal organic framework composite material and titanium dioxide;

[0062] (3) Add 200 mL of 4% sodium hydroxide solution and 9.0 g of calcium carbonate powder into a three-necked flask, stir at 65°C for 0.75 h, wash with water until neutral and filter, vacuum dry the pretreated calcium carbonate, and set aside the alkali-washed calcium carbonate powder. Prepare 200 mL of ethanol aqueous solution containing KH560, add the alkali-washed calcium carbonate powder, and stir at 65°C for 1.5 h. In the ethanol aqueous solution containing KH560, the volume ratio of KH560, water and anhydrous ethanol is 1:3:6. The modified treatment of KH560 further enhances the dispersibility of the alkali-washed calcium carbonate powder in the organic medium, which is conducive to a better subsequent coating effect. Filter and wash with anhydrous ethanol for 4 times. The filter cake is vacuum dried to obtain KH560 modified alkali-washed calcium carbonate powder. Then, the combined filler of graphene oxide metal organic framework composite material and titanium dioxide described in step (2) is added to 150 mL of deionized water, ultrasonicated for 25 min, and added with KH560 modified The alkali-washed calcium carbonate powder was stirred at 75°C for 1.5 hours, and separated by standing with a separatory funnel. The upper suspension was filtered, washed with water for 4 times, and vacuum dried. The combined filler of graphene oxide metal organic framework composite material and titanium dioxide was dispersed in an aqueous medium, and then adsorbed onto the surface of KH560 modified alkali-washed calcium carbonate powder, forming a coating of KH560 modified alkali-washed calcium carbonate powder by the combined filler of graphene oxide metal organic framework composite material and titanium dioxide. The prepared integrated composite material of pigment and filler can reduce the agglomeration phenomenon caused by differences in density, particle size and surface properties, and improve the uniform dispersibility of the composite material in water-based acrylic resin, and give full play to the maximized role of titanium dioxide, calcium carbonate powder and graphene oxide metal organic framework composite material as combined fillers, and improve the crosslinking density with the resin in multiple dimensions, which is helpful to improve wear resistance, water resistance and aging resistance, and obtain a pigment-coated combined integrated filler.

[0063] This embodiment provides a method for preparing an environmentally friendly water-based composite coating for road markings, which specifically comprises the following steps:

[0064] S1. The MOS2 powder is mechanically ball-milled by a high-speed vibration ball mill. During the mechanical ball-milling process, the ball-milling speed is 11000 rpm and the ball-milling time is 80 min. The MOS2 flakes are effectively peeled off by ball-milling treatment, thereby increasing the specific surface area and increasing the number of active sites. The treated MOS2 powder is then added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, and then ultrasonicated for 1.5 h using an ultrasonic cleaner. After standing for 9 h, the well-dispersed upper solution is collected and placed in an oven for drying. The powder after sieving has a smaller particle size and a more uniform distribution. The obtained nano-MOS2 powder after sieving is added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, fully stirred, and then ultrasonicated for 7.5 min using an ultrasonic cell crusher, which further ensures the excellent dispersibility and stability of nano-MOS2 in water-based acrylic resin, and is conducive to the improvement of the wear resistance, adhesion, durability and anti-aging properties of the resin by nano-MOS2, thereby obtaining a nano-MOS2 aqueous dispersion.

[0065] S2, adding the nano-MOS2 aqueous dispersion described in step S1 into a three-necked flask, heating to 120°C, weighing 8.0g acrylic acid, 20.0g butyl methacrylate, 30.5g methyl methacrylate, 12.0g hydroxypropyl acrylate, 0.5g tert-butyl perbenzoate, and 3.0g 2,4-diphenyl-4-methyl-1-pentene, respectively, mixing evenly, and then dropping into the three-necked flask, the dropping time is 2.5h, and the reaction is kept warm for 0.75h, and then cooled to 80°C, 0.5g N,N-dimethylethanolamine is added and neutralized for 15min, and nano-MOS2 is introduced into the process of preparing water-based acrylic resin from acrylic monomers. The nano-MOS2 aqueous dispersion is modified, wherein the nano-MOS2 has excellent strength and hardness, and can significantly improve the wear resistance of the water-based acrylic resin. The nano-MOS2 also has good chemical stability and weather resistance, and can improve the weather resistance and anti-aging properties of the water-based acrylic resin, so that it can maintain good performance under various climatic conditions. The sulfur atom in the nano-MOS2 acts as a catalyst, which can accelerate the polymerization reaction of the resin and improve the reaction efficiency. The sulfur atom also has heat resistance and chemical resistance, etc., which contributes to the stability of the polymerization product. Thus, the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion is obtained;

[0066] S3, adding the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion described in step S2 into a stirrer, stirring at a speed of 450 rpm for 7.5 min, adding 902W defoamer, 4100 wetting agent, BYK333 leveling agent, stirring for 4 min, and then adding the pigment-coated combined integrated filler in small amounts and multiple times. After adding, adjusting the speed to 900 rpm and stirring for 15 min, then reducing the speed to 600 rpm, and then adding propylene glycol phenyl ether and water. Propylene glycol phenyl ether is used as a film-forming agent to reduce the content of volatile organic matter in the coating and give the coating better agglomeration performance. After all components are added, adjusting the speed to 900 rpm and stirring for 15 min. The pigment-coated combined integrated filler is in the nano-MOS2 aqueous dispersion. The dispersion modified water-based acrylic resin can be evenly dispersed, and the catalytic effect can effectively improve the crosslinking density and curing process with the resin, which not only shortens the drying time, but also improves the surface strength and hardness, heat resistance and stability through the formed dense structure, and reduces the penetration of water, thereby significantly improving the wear resistance, water resistance and aging resistance, and extending the service life of the coating. Among them, in the water-based acrylic resin modified by the nano-MOS2 water dispersion, the nano-MOS2 can form a good interface with other components in the coating, enhance the adhesion and bonding force of the coating, and better resist external wear, rain erosion and high temperature, thereby reducing the occurrence of coating peeling, shedding and cracking, and obtaining an environmentally friendly road sign water-based composite coating.

[0067] Example 4

[0068] This embodiment proposes an environmentally friendly water-based composite coating for road signs, comprising the following components in parts by weight: 80 parts of water-based acrylic resin modified by nano-MOS2 aqueous dispersion, 30 parts of pigment-coated combined integrated filler, 5 parts of 902W defoamer, 8 parts of 4100 wetting agent, 8 parts of BYK333 leveling agent, 3 parts of propylene glycol phenyl ether, and 20 parts of water.

[0069] The pigment-coated combined integrated filler comprises the following components in parts by weight: 5 parts of graphene oxide metal organic framework composite material, 10 parts of titanium dioxide, and 10 parts of calcium carbonate powder.

[0070] The nano-MOS2 water dispersion modified water-based acrylic resin comprises the following components in parts by weight: 15 parts of the nano-MOS2 water dispersion and 80 parts of the water-based acrylic resin.

[0071] The preparation method of the pigment-coated combined integrated filler specifically comprises the following steps:

[0072] (1) 0.1 g of graphene oxide powder was washed with methanol for 5 times and then added to 20 mL of methanol solution. Then, anhydrous cobalt acetate solid was added to the methanol solution containing graphene oxide, stirred thoroughly and set aside. The amount of anhydrous cobalt acetate added was 1.0 g. Cobalt ions acted as a catalyst to increase the crosslinking density and curing time of the resin, which not only shortened the construction period but also ensured the quality and durability of the coating after curing. Then, 2.0 g of 2-methylimidazole was dissolved in 20 mL of methanol solution and then dropped into the methanol solution containing graphene oxide and anhydrous cobalt acetate. The growth of metal organic framework ZIF-67 nanoparticles on the surface of graphene oxide sheets was achieved at a speed of 200 rpm. Stirring for 20 minutes, standing for 24 hours, centrifuging, washing the precipitate with methanol solution for 5 times, and vacuum drying, a composite material of graphene oxide and ZIF-67 is generated through this process, which not only reduces the aggregation of graphene oxide nanosheets, improves the dispersibility and compatibility of the composite material in the water-based acrylic resin matrix, but also can play the role of ZIF-67 as a curing agent, can react with the functional groups in the water-based acrylic resin to form a cross-linked structure, accelerate the curing process of the resin, and help to improve the hardness, heat resistance and water resistance of the water-based acrylic resin, can better resist the adverse effects of wear, aging and rain, improve durability, and obtain a graphene oxide metal organic framework composite material;

[0073] (2) Dissolve 10.0 g of titanium dioxide and 20 mL of KH560 in 100 mL of methanol solution, and heat the reaction at 45 °C for 12 h under constant temperature condensation reflux. Then, disperse the graphene oxide metal organic framework composite material described in step (1) in 20 mL of deionized water, and then add the methanol solution containing titanium dioxide and KH560. React at room temperature for 10 h and dry in an oven. The addition of graphene oxide and metal organic framework composite material improves the dispersibility and fluidity of titanium dioxide, and can obtain a better coating effect, thereby obtaining a composite filler of graphene oxide metal organic framework composite material and titanium dioxide.

[0074] (3) Add 200 mL of 4% sodium hydroxide solution and 10.0 g of calcium carbonate powder into a three-necked flask, stir at 70°C for 0.5 h, wash with water until neutral and filter, vacuum dry the pretreated calcium carbonate, and set aside the alkali-washed calcium carbonate powder. Prepare 200 mL of ethanol aqueous solution containing KH560, add the alkali-washed calcium carbonate powder, and stir at 70°C for 1 h. In the ethanol aqueous solution containing KH560, the volume ratio of KH560, water and anhydrous ethanol is 1:3:6. The modified treatment of KH560 further enhances the dispersibility of the alkali-washed calcium carbonate powder in the organic medium, which is conducive to a better subsequent coating effect. Filter and wash with anhydrous ethanol for 5 times. The filter cake is vacuum dried to obtain KH560 modified alkali-washed calcium carbonate powder. Then, the combined filler of graphene oxide metal organic framework composite material and titanium dioxide described in step (2) is added to 150 mL of deionized water, ultrasonicated for 20 min, and added with KH560 modified The alkali-washed calcium carbonate powder was stirred at 80°C for 1 hour, and separated by standing with a separatory funnel. The upper suspension was filtered, washed with water for 5 times, and vacuum dried. The combined filler of graphene oxide metal organic framework composite material and titanium dioxide was dispersed in an aqueous medium, and then adsorbed onto the surface of KH560 modified alkali-washed calcium carbonate powder, forming a coating of KH560 modified alkali-washed calcium carbonate powder by the combined filler of graphene oxide metal organic framework composite material and titanium dioxide. The prepared integrated composite material of pigment and filler can reduce the agglomeration phenomenon caused by differences in density, particle size and surface properties, and improve the uniform dispersibility of the composite material in water-based acrylic resin, and give full play to the maximized role of titanium dioxide, calcium carbonate powder and graphene oxide metal organic framework composite material as combined fillers, and improve the crosslinking density with the resin in multiple dimensions, which is helpful to improve wear resistance, water resistance and aging resistance, and obtain a pigment-coated combined integrated filler.

[0075] This embodiment provides a method for preparing an environmentally friendly water-based composite coating for road markings, which specifically comprises the following steps:

[0076] S1. The MOS2 powder is mechanically ball-milled by a high-speed vibration ball mill. During the mechanical ball-milling process, the ball-milling speed is 12000 rpm and the ball-milling time is 70 min. The MOS2 flakes are effectively peeled off by ball-milling treatment, thereby increasing the specific surface area and increasing the number of active sites. The treated MOS2 powder is then added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, and then ultrasonicated for 1 h using an ultrasonic cleaning machine. After standing for 8 h, the well-dispersed upper solution is collected and placed in an oven for drying. The powder after sieving has a smaller particle size and a more uniform distribution. The obtained nano-MOS2 powder after sieving is added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, fully stirred, and then ultrasonicated for 5 min using an ultrasonic cell crusher, which further ensures the excellent dispersibility and stability of nano-MOS2 in water-based acrylic resin, and is conducive to the improvement of the wear resistance, adhesion, durability and anti-aging properties of the resin by nano-MOS2, thereby obtaining a nano-MOS2 aqueous dispersion.

[0077] S2, adding the nano-MOS2 aqueous dispersion described in step S1 into a three-necked flask, heating to 130°C, weighing 8.0g acrylic acid, 20.0g butyl methacrylate, 40.0g methyl methacrylate, 12.0g hydroxypropyl acrylate, 0.5g tert-butyl perbenzoate, and 3.0g 2,4-diphenyl-4-methyl-1-pentene, respectively, mixing evenly, and then dropping into the three-necked flask, the dropping time is 2h, and the temperature is kept for reaction for 0.5h, and then cooled to 80°C, 0.5g N,N-dimethylethanolamine is added and neutralized for 10min, and nano-MOS2 is introduced into the process of preparing water-based acrylic resin from acrylic monomers. OS2 aqueous dispersion is modified, wherein nano-MOS2 has excellent strength and hardness, can significantly improve the wear resistance of water-based acrylic resin, nano-MOS2 also has good chemical stability and weather resistance, can improve the weather resistance and anti-aging performance of water-based acrylic resin, so that it can maintain good performance under various climatic conditions, and the sulfur atom in nano-MOS2 as a catalyst can accelerate the polymerization reaction of the resin and improve the reaction efficiency, the sulfur atom also has heat resistance and chemical resistance, etc., which is conducive to the stability of the polymerization product, and the nano-MOS2 aqueous dispersion modified water-based acrylic resin is obtained;

[0078] S3, adding the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion described in step S2 into a stirrer, stirring at a speed of 500 rpm for 5 min, adding 902W defoamer, 4100 wetting agent, BYK333 leveling agent, stirring for 3 min, and then adding the pigment-coated combined integrated filler in small amounts and multiple times. After adding, adjusting the speed to 1000 rpm and stirring for 10 min, then reducing the speed to 600 rpm, and then adding propylene glycol phenyl ether and water. Propylene glycol phenyl ether is used as a film-forming agent to reduce the content of volatile organic matter in the coating and give the coating better agglomeration performance. After all components are added, adjusting the speed to 1000 rpm and stirring for 10 min. The pigment-coated combined integrated filler is in the nano-MOS2 aqueous dispersion. The dispersion modified water-based acrylic resin can be evenly dispersed, and the catalytic effect can effectively improve the crosslinking density and curing process with the resin, which not only shortens the drying time, but also improves the surface strength and hardness, heat resistance and stability through the formed dense structure, and reduces the penetration of water, thereby significantly improving the wear resistance, water resistance and aging resistance, and extending the service life of the coating. Among them, in the water-based acrylic resin modified by the nano-MOS2 water dispersion, the nano-MOS2 can form a good interface with other components in the coating, enhance the adhesion and bonding force of the coating, and better resist external wear, rain erosion and high temperature, thereby reducing the occurrence of coating peeling, shedding and cracking, and obtaining an environmentally friendly road sign water-based composite coating.

[0079] Comparative Example 1

[0080] This comparative example provides an environmentally friendly water-based composite coating for road signs, which differs from Example 1 in that the pigment-coated combined integrated filler does not contain graphene oxide metal-organic framework composite materials; the preparation method of the pigment-coated combined integrated filler is completely different from that of Example 1, which is only a simple mixture of titanium dioxide and calcium carbonate powder; the preparation method of the environmentally friendly water-based composite coating for road signs is the same as that of Example 1.

[0081] Comparative Example 2

[0082] This comparative example provides an environmentally friendly water-based composite coating for road signs, which differs from Example 1 in that the pigment-coated combined integrated filler does not contain anhydrous cobalt acetate and 2-methylimidazole; anhydrous cobalt acetate and 2-methylimidazole are not added in step (1) of the preparation method of the pigment-coated combined integrated filler; the preparation method of the environmentally friendly water-based composite coating for road signs is the same as that of Example 1.

[0083] Comparative Example 3

[0084] This comparative example provides an environmentally friendly water-based composite coating for road signs, which differs from Example 1 in that the environmentally friendly water-based composite coating for road signs does not contain nano-MOS2 aqueous dispersion; the preparation method of the pigment-coated combined integrated filler is the same as that of Example 1; the preparation method of the environmentally friendly water-based composite coating for road signs does not include step S1.

[0085] Experimental Example 1

[0086] Non-stick tire drying time experiment

[0087] Test sample: the environmentally friendly road marking water-based composite coating prepared in Examples 1-4 and Comparative Examples 1-3.

[0088] Test method: Place the scraper at the center of the long side of a 200mm×150mm×5mm cement asbestos board, and immediately pour the test sample into the scraper, then move the scraper horizontally to make a layer parallel to the short side of the cement asbestos board, with a thickness of 1.5-2.0mm and a width of 80mm. Immediately after the preparation is completed, press the stopwatch to start timing. Test after 3 minutes. Roll the measuring instrument from the center of one end of the short side of the test board to the other end for 1s. Avoid applying external force to the coating during rolling. Then visually inspect the tire of the measuring instrument for sticky test material. If there is sticky, wipe it clean with a cotton cloth moistened with acetone. Repeat the experiment every 30s until the tire is no longer sticky to the test material. Stop the stopwatch. This time is the non-stick tire drying time (min).

[0089] Figure 2 The non-stick tire drying time result diagram of Examples 1-4 and Comparative Examples 1-3; as shown in the figure, the non-stick tire drying time of Examples 1-4 is 5.5-7min, indicating that the drying time is short; the non-stick tire drying time of Comparative Examples 1-3 is 9.5-13min, indicating that the drying time is long; the pigment-coated combined integrated filler of Comparative Example 1 does not contain graphene oxide metal organic framework composite material, and cannot form an integrated composite material of pigment and filler, which is not conducive to the dispersion uniformity of titanium dioxide and calcium carbonate powder, thereby having an adverse effect on the drying rate of the coating, and is not conducive to promoting the cross-linking reaction with the resin, resulting in a long drying time; Comparative Example 1 The pigment-coated combined integrated filler of Example 2 does not contain anhydrous cobalt acetate and 2-methylimidazole, which not only increases the aggregation of graphene oxide, but also fails to form a ZIF-67 metal organic framework material with catalytic curing effect, which is not conducive to increasing the crosslinking density with the resin and accelerating the curing process, resulting in a long drying time; the environmentally friendly road sign water-based composite coating of Comparative Example 3 does not contain nano-MOS2 water dispersion, and cannot exert the crosslinking effect of nano-MOS2 on water-based acrylic acid, nor is it conducive to forming strong chemical bonds with the pigment-coated combined integrated filler and other materials, which is not conducive to enhancing the crosslinking reaction and curing rate of the coating, resulting in a long drying time.

[0090] Experimental Example 2

[0091] Wear resistance test

[0092] Test sample: the environmentally friendly road marking water-based composite coating prepared in Examples 1-4 and Comparative Examples 1-3.

[0093] Test method: Determine the wear amount (mg) of the test sample according to GB / T1768-2006 "Determination of abrasion resistance of paints and varnishes - Rotating rubber grinding wheel method".

[0094] Figure 3 It is a graph of the wear results of Examples 1-4 and Comparative Examples 1-3; as shown in the figure, the wear amount of Examples 1-4 is 8-13 mg, indicating that the wear resistance is strong; the wear amount of Comparative Examples 1-3 is 18-23 mg, indicating that the wear resistance is weak; the pigment-coated combined integrated filler of Comparative Example 1 does not contain graphene oxide metal-organic framework composite materials, and cannot form an integrated composite material of pigment and filler, which is not conducive to the dispersion compatibility of the materials, nor is it conducive to increasing the cross-linking density of the resin, resulting in weak wear resistance; the pigment-coated combined integrated filler of Comparative Example 2 does not contain anhydrous cobalt acetate and 2-methylimidazole, and cannot reduce the agglomeration of graphene oxide to limit its role, and cannot further catalyze the cross-linking reaction between the integrated filler and the functional groups in the resin, which is not conducive to forming a dense network structure, resulting in weak wear resistance; the environmentally friendly road sign water-based composite coating of Comparative Example 3 does not contain nano-MOS2 aqueous dispersion, and cannot enhance the adhesion and bonding of the coating through nano-MOS2, resulting in weak wear resistance.

[0095] Experimental Example 3

[0096] Water resistance and aging resistance test

[0097] Test sample: the environmentally friendly road marking water-based composite coating prepared in Examples 1-4 and Comparative Examples 1-3.

[0098] Test method:

[0099] (1) Water resistance: Prepare the test sample into a 60mm×60mm×5mm specimen and place it in a glass water tank filled with deionized water according to GB / T1733 "Determination of water resistance of paint film". Make sure that two-thirds of the length of the specimen is immersed in water and keep the water temperature at about 20-25℃. When discoloration, bubbles, wrinkles, shedding, rust, etc. appear on the surface, take it out and record the immersion time, which is the water resistance time (h);

[0100] (2) Aging resistance: The test samples are tested in accordance with GB / T14522-2008 "Artificial climate accelerated test methods for plastic and rubber materials for mechanical industrial products". UVB-313 aging equipment is used to irradiate at 60°C to simulate the aging phenomenon of the marking coating under high temperature and dry conditions. When the surface shows discoloration, wrinkling, shedding, cracking, etc., the test is stopped. This is the aging time (h).

[0101] Figure 4 The water resistance time results of Examples 1-4 and Comparative Examples 1-3 are shown in FIG. Figure 5 The aging time results of Examples 1-4 and Comparative Examples 1-3 are shown in FIG. Figure 4 The water resistance time of Examples 1-4 is 82-96h. Figure 5 , the aging time of Examples 1-4 is 152-168h, indicating that the water resistance and aging resistance are better; Figure 4 The water resistance time of comparative examples 1-3 is 52-63h. Figure 5 The aging time of comparative examples 1-3 is 120-132h, indicating that the water resistance and aging resistance are average; the pigment-coated combined integrated filler of comparative example 1 does not contain graphene oxide metal organic framework composite material, and cannot play the role of water barrier penetration by compact lamellar structure, nor can it form a coating on the filler by the composite material with heat-resistant stability, which is not conducive to the aging resistance of the coating at high temperature, resulting in average water resistance and aging resistance; the pigment-coated combined integrated filler of comparative example 2 does not contain anhydrous cobalt acetate and 2-methylimidazole, which is not conducive to enhancing the crosslinking density of the coating, It is impossible to form a dense and stable cross-linked structure, which is not conducive to blocking the adverse effects of moisture and high temperature on the coating, resulting in average water resistance and aging resistance; the environmentally friendly road sign water-based composite coating of Comparative Example 3 does not contain nano-MOS2 aqueous dispersion, and cannot form a good interface bonding with other components in the coating through nano-MOS2, which is not conducive to the adhesion and bonding of the coating, and cannot play the stabilizing role of molybdenum atoms in high temperature environments, which is not conducive to enhancing the density and stability of the coating, and thus cannot effectively resist the adverse effects of moisture and high temperature on the coating after curing, resulting in average water resistance and aging resistance.

[0102] The above experimental results show that the drying time, wear resistance, water resistance and aging resistance of Examples 1-4 of the present invention are significantly better than those of Comparative Examples 1-3. Among them, Example 1, which uses a pigment-coated combined integrated filler and a nano-MOS2 aqueous dispersion to modify the water-based acrylic resin, has a shorter drying time and better wear resistance, water resistance and aging resistance. The water-based acrylic resin is modified with a nano-MOS2 aqueous dispersion and then a pigment-coated combined integrated filler is added, which reduces the agglomeration problem caused by the separate use of pigments and fillers, improves the dispersion compatibility and bonding of the components in the coating, effectively shortens the drying time, forms a dense and stable coating structure, significantly improves the wear resistance, water resistance and aging resistance of the coating, and extends its service life.

[0103] While the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that many changes, modifications, substitutions and variations can be made to the embodiments without departing from the principles and spirit of the invention.

[0104] The present invention and its implementation methods are described above, which is not restrictive. The drawings are only one of the implementation methods of the present invention, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it and design methods and embodiments similar to the technical solution without creativity without departing from the purpose of the invention, they should all fall within the protection scope of the present invention.

Claims

1. An environmentally friendly water-based composite coating for road signs, characterized by: The environmentally friendly road sign water-based composite coating comprises the following components in parts by weight: 60-80 parts of water-based acrylic resin modified by nano-MOS2 water dispersion, 30-50 parts of pigment-coated combined integrated filler, 3-5 parts of 902W defoamer, 5-8 parts of 4100 wetting agent, 5-8 parts of BYK333 leveling agent, 3-5 parts of propylene glycol phenyl ether, and 10-20 parts of water; the pigment-coated combined integrated filler comprises the following components in parts by weight: 5-8 parts of graphene oxide metal organic framework composite material, 8-10 parts of titanium dioxide, and 8-10 parts of calcium carbonate powder; the water-based acrylic resin modified by nano-MOS2 water dispersion comprises the following components in parts by weight: 15-25 parts of nano-MOS2 water dispersion and 70-80 parts of water-based acrylic resin.

2. A method for preparing the environmentally friendly water-based composite coating for road markings according to claim 1, characterized in that: The specific steps include: S1. The MOS2 powder is mechanically ball-milled by a high-speed vibration ball mill, and then the treated MOS2 powder is mixed with 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, and then ultrasonicated for 1-2 hours using an ultrasonic cleaner. After standing for 8-10 hours, the well-dispersed upper solution is collected and placed in an oven for drying. The sieved nano-MOS2 powder is added to 200 mL of deionized water containing 0.04 g of sodium dodecyl sulfate, stirred thoroughly, and then ultrasonicated for 5-10 minutes using an ultrasonic cell crusher to obtain a nano-MOS2 aqueous dispersion; S2, adding the nano-MOS2 aqueous dispersion described in step S1 into a three-necked flask, heating to 110-130°C, weighing 8.0g acrylic acid, 20.0g butyl methacrylate, 30.0-40.0g methyl methacrylate, 12.0g hydroxypropyl acrylate, 0.5g tert-butyl perbenzoate, and 3.0g 2,4-diphenyl-4-methyl-1-pentene respectively, mixing evenly, and then dropping into the three-necked flask, the dropping time is 2-3h, and then keeping warm for reaction for 0.5-1h, cooling to 80°C, adding 0.5g N,N-dimethylethanolamine for neutralization for 10-20min, and obtaining a water-based acrylic resin modified by the nano-MOS2 aqueous dispersion; S3, adding the water-based acrylic resin modified by the nano-MOS2 aqueous dispersion described in step S2 into a mixer, stirring at a speed of 400-500 rpm for 5-10 min, adding 902W defoamer, 4100 wetting agent, BYK333 leveling agent, stirring for 3-5 min, and then adding the pigment-coated combined integrated filler in small amounts and multiple times, adjusting the speed to 800-1000 rpm and stirring for 10-20 min after adding, then reducing the speed to 600 rpm, and then adding propylene glycol phenyl ether and water. After all the components are added, adjusting the speed to 800-1000 rpm and stirring for 10-20 min to obtain an environmentally friendly road sign water-based composite coating.

3. The method for preparing the environmentally friendly water-based composite coating for road markings according to claim 2, characterized in that: In step S1, during the mechanical ball milling process, the ball milling speed is 10000-12000 rpm, and the ball milling time is 70-90 min.

4. The method for preparing the environmentally friendly water-based composite coating for road markings according to claim 3, characterized in that: The method for preparing the pigment-coated combined integrated filler specifically comprises the following steps: (1) 0.1-0.3 g of graphene oxide powder was washed with methanol for 3-5 times and then added to 20 mL of methanol solution, then anhydrous cobalt acetate solid was added to the methanol solution containing graphene oxide, fully stirred and set aside, then 2.0 g of 2-methylimidazole was dissolved in 20 mL of methanol solution, and then the solution was dropped into the methanol solution containing graphene oxide and anhydrous cobalt acetate, stirred at 100-200 rpm for 20-30 min, allowed to stand for 24 h, centrifuged, and the precipitate was washed with methanol solution for 3-5 times, and vacuum dried to obtain a graphene oxide metal organic framework composite material; (2) Dissolve 8.0-10.0 g of titanium dioxide and 20-30 mL of KH560 in 100 mL of methanol solution, react at a temperature of 40-45° C., and reflux at a constant temperature for 12 h. Set aside, then disperse the graphene oxide metal organic framework composite material described in step (1) in 20 mL of deionized water, then add the methanol solution containing titanium dioxide and KH560, react at room temperature for 10-12 h, and dry in an oven to obtain a composite filler of the graphene oxide metal organic framework composite material and titanium dioxide; (3) Add 200 mL of 4% sodium hydroxide solution and 8.0-10.0 g of calcium carbonate powder into a three-necked flask, stir at 60-70°C for 0.5-1 h, then wash with water until neutral and filter. The pretreated calcium carbonate is vacuum dried and the alkali-washed calcium carbonate powder is ready for use. Prepare 200 mL of ethanol aqueous solution containing KH560, add the alkali-washed calcium carbonate powder, stir at 60-70°C for 1-2 h, filter and wash with anhydrous ethanol for 3-5 times. The mixture was dried in vacuo to obtain KH560 modified alkali-washed calcium carbonate powder; the graphene oxide metal organic framework composite material and titanium dioxide composite filler described in step (2) were added to 150 mL of deionized water, ultrasonicated for 20-30 min, KH560 modified alkali-washed calcium carbonate powder was added, stirred at 70-80° C. for 1-2 h, separated by standing with a separatory funnel, the upper suspension was filtered, washed with water for 3-5 times, and dried in vacuo to obtain a pigment-coated combined integrated filler.

5. The method for preparing the environmentally friendly water-based composite coating for road markings according to claim 4, characterized in that: In step (1), the amount of anhydrous cobalt acetate added is 1.0-2.0 g.

6. The method for preparing the environmentally friendly water-based composite coating for road markings according to claim 5, characterized in that: In step (3), in the ethanol aqueous solution containing KH560, the volume ratio of KH560, water and anhydrous ethanol is 1:3:6.

Images