Acrylic acid composite anti-freezing coating as well as preparation method and application thereof

Abstract

The invention discloses an acrylic acid composite anti-freezing coating as well as a preparation method and application thereof, and belongs to the technical field of road engineering materials. The acrylic acid composite anti-freezing coating prepared by the invention comprises the following raw material components in percentage by mass: 20%-35% of acrylic resin, 15%-25% of a composite anti-freezing agent, 1%-5% of nano titanium dioxide, 2%-3% of nano silicon dioxide, 1%-5% of an auxiliary agent and 30%-50% of an environment-friendly solvent, the composite anti-freezing agent is obtained by coating a diatomite anti-freezing agent with a methyl acrylate polymer; the methyl acrylate polymer is obtained by compounding methyl acrylate and unsaturated quaternary ammonium salt; the unsaturated quaternary ammonium salt is obtained by reacting 5-chloro-2-hydroxybenzophenone with N, N-diallylethanolamine and then reacting with a brominated aliphatic chain; the acrylic acid composite anti-freezing coating prepared by the invention has good anti-freezing property, durability and wear resistance.

Description

Technical Field

[0001] This invention relates to the field of road engineering materials technology, specifically to an acrylic composite anti-icing coating, its preparation method, and its application. Background Technology

[0002] In winter, icy roads are a widespread problem that seriously threatens traffic safety. Ice cover drastically reduces the friction coefficient between the road surface and vehicle tires, leading to a significant increase in braking distance and greatly increasing the risk of chain-reaction collisions and other serious traffic accidents, posing a huge threat to people's lives and property. Currently, the mainstream measures to deal with icy roads include spreading de-icing agents and mechanical de-icing, but both have significant drawbacks: while de-icing agents are fast-acting, they bring serious environmental negative effects, such as corroding bridges and road facilities, damaging soil structure, inhibiting plant growth, and polluting groundwater systems; mechanical de-icing is limited by operational efficiency, and the rigid removal process can easily cause physical damage to the road surface. Therefore, developing an anti-icing material that is environmentally friendly, highly efficient, and long-lasting has become an urgent need in the field of traffic engineering.

[0003] In recent years, anti-icing coatings have attracted much attention as a new type of active protective material. Among them, acrylic coatings, with their excellent film-forming properties, weather resistance, and chemical corrosion resistance, have shown broad application prospects in the field of road coatings. However, traditional acrylic coatings still face severe challenges in practical applications: on the one hand, their anti-icing performance is limited, making it difficult to effectively inhibit ice crystal nucleation and growth in extreme low temperature and high humidity environments, thus failing to meet actual anti-skid requirements; on the other hand, the road service environment is complex and variable, with coatings exposed to strong ultraviolet radiation, drastic temperature changes, and high-frequency rolling friction from vehicle tires for extended periods. Traditional formulations often lack effective reinforcement and modification mechanisms, making them prone to photo-oxidative aging, chalking and peeling, or premature failure due to insufficient wear resistance, thus hindering long-term service life.

[0004] Therefore, how to significantly improve the anti-icing performance of acrylic composite anti-icing coatings while simultaneously enhancing their anti-aging ability and wear resistance is a key technical problem that urgently needs to be solved. Summary of the Invention

[0005] The purpose of this invention is to provide an acrylic composite anti-icing coating, its preparation method, and its application, so as to solve the technical problems mentioned in the background art.

[0006] The technical solution to achieve the objective of this invention is: In a first aspect, the present invention provides an acrylic composite anti-icing coating, the raw material components of which include 20%~35% acrylic resin, 15%~25% composite anti-icing agent, 1%~5% nano titanium dioxide, 2%~3% nano silica, 1%~5% additives, and 30%~50% environmentally friendly solvent.

[0007] Furthermore, the acrylic resin is selected from acrylic resins with a molecular weight between 50,000 and 80,000 and a glass transition temperature between -20 and 30°C. It can form a tough paint film at room temperature, while still having a certain degree of flexibility and not easily cracking at low temperatures. Furthermore, the particle size of the nano-titanium dioxide is 15~45nm, and the particle size of the nano-silica is 10~25nm.

[0008] Furthermore, the additives include dispersants, defoamers, and thickeners; the dispersants are used to uniformly disperse the components and ensure the stability of the coating; the defoamers are used to eliminate bubbles generated during the coating preparation process and improve the quality of the coating; and the thickeners are used to adjust the viscosity of the coating to facilitate application.

[0009] Furthermore, the environmentally friendly solvent is selected from environmentally friendly organic solvents, including ethyl acetate and propylene glycol methyl ether acetate; these solvents can effectively dissolve acrylic resins and have low volatile organic compound (VOC) content, meeting environmental protection requirements.

[0010] Furthermore, the composite anti-de-icing agent is obtained by coating diatomaceous earth anti-de-icing agent with methyl acrylate polymer; the diatomaceous earth anti-de-icing agent is obtained by combining diatomaceous earth with chloride salts; the chloride salts include sodium chloride and potassium chloride.

[0011] Furthermore, the methyl acrylate polymer is obtained by polymerizing methyl acrylate with an unsaturated quaternary ammonium salt.

[0012] Furthermore, the unsaturated quaternary ammonium salt is obtained by reacting 5-chloro-2-hydroxybenzophenone with N,N-diallylethanolamine and then reacting it with a brominated aliphatic chain; the brominated aliphatic chain includes bromooctane.

[0013] In a second aspect, the present invention provides a method for preparing an acrylic composite anti-icing coating as described in the first aspect, comprising the following steps: (1) Weigh and prepare each raw material component, and dry the nano titanium dioxide and nano silicon dioxide; (2) Add environmentally friendly solvent to the reactor, and add acrylic resin, composite anti-icing agent, nano titanium dioxide, nano silica and additives in sequence under stirring conditions, and stir for 30~60min; (3) Transfer the mixed material from step (2) to an ultrasonic dispersion device and ultrasonically disperse for 1-2 hours; (4) Filter the material after ultrasonic dispersion in step (3) to obtain acrylic composite anti-icing coating.

[0014] Further, the preparation steps of the composite anti-de-icing agent are as follows: First, mix 5-6 parts by weight of KH-570 with 0.7-0.8 parts by weight of concentrated hydrochloric acid, stir and heat to 70-85°C, then add 4-5 parts by weight of deionized water dropwise over 30 minutes, and react at a constant temperature for 110-130 minutes after the addition is complete; then add 86-90 parts by weight of toluene, heat to boiling and distill at 105°C to remove alcohol, water and hydrochloric acid from the solution; heat to 110-120°C, add 4.6-5.5 parts by weight of diatomaceous earth anti-de-icing agent, and react under constant temperature and stirring under reflux for 4-6 hours; then add 0.07-0.08 parts by weight of initiator benzoyl peroxide, and slowly add 2.3-2.4 parts by weight of methyl acrylate and 2.9-3.8 parts by weight of unsaturated quaternary ammonium salt over 30 minutes, and continue the reaction for 3-4 hours; finally, after filtration, drying and grinding, the composite anti-de-icing agent is obtained.

[0015] Further, the preparation method of the diatomaceous earth anti-coagulation agent is as follows: anhydrous ethanol, emulsifier OP-10, and diatomaceous earth are mixed and ultrasonically dispersed at a mass ratio of (78~80):1:(2.2~2.4) for at least 30 minutes to obtain a diatomaceous earth ethanol suspension; a saturated potassium chloride aqueous solution is heated to 58~62℃ and hydrochloric acid solution is added dropwise to adjust the pH to 1, and then added dropwise to the diatomaceous earth ethanol suspension at a volume ratio of 4:1 under ultrasonic oscillation to form a precipitate, which is then filtered, dried, ground, and dried for later use to obtain the diatomaceous earth anti-coagulation agent.

[0016] Further, the preparation method of the unsaturated quaternary ammonium salt is as follows: Under nitrogen protection, N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, and acetone are mixed and stirred for 30-60 min. Then, 5-chloro-2-hydroxybenzophenone is added, and the mixture is heated, stirred, refluxed, and cooled for 11-13 h. After removing excess potassium carbonate and acetone, brominated aliphatic chains are added and the temperature is raised to 110-120 °C. The mixture is then heated, stirred, refluxed, and cooled for 3-4 h to obtain the unsaturated quaternary ammonium salt.

[0017] The preparation process of an unsaturated quaternary ammonium salt is as follows: Further, the molar ratio of N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, 5-chloro-2-hydroxybenzophenone, and brominated aliphatic chain is 5:(0.0005~0.001):(6~7):(5~10):(6~8); the mass ratio of N,N-diallylethanolamine to acetone is 1:(6~12).

[0018] Thirdly, the present invention provides an application of the acrylic composite anti-icing coating as described in the first aspect, wherein the acrylic composite anti-icing coating is applied to the field of road anti-icing; the road includes asphalt mixture pavement and cement concrete pavement.

[0019] By adopting the above technical solution, the present invention has the following beneficial effects: (1) The acrylic composite anti-icing coating of the present invention comprises, by mass percentage, 20% to 35% acrylic resin, 15% to 25% composite anti-icing agent, 1% to 5% nano titanium dioxide, 2% to 3% nano silica, 1% to 5% additives, and 30% to 50% environmentally friendly solvent; wherein, acrylic resin, as the film-forming substance of the coating, provides good adhesion and weather resistance; the addition of composite anti-icing agent endows the acrylic composite anti-icing coating with excellent anti-icing performance while effectively improving the anti-aging performance of the acrylic composite anti-icing coating; the addition of nano titanium dioxide and nano silica further improves the strength, wear resistance and anti-aging performance of the coating.

[0020] (2) The composite anti-de-icing agent of the present invention is obtained by coating diatomaceous earth anti-de-icing agent with methyl acrylate polymer; the diatomaceous earth anti-de-icing agent is obtained by compounding diatomaceous earth with chloride salt; the chloride salt includes sodium chloride and potassium chloride; the methyl acrylate polymer is obtained by polymerizing methyl acrylate with unsaturated quaternary ammonium salt; the unsaturated quaternary ammonium salt is obtained by reacting 5-chloro-2-hydroxybenzophenone with N,N-diallylethanolamine and then reacting with brominated aliphatic chains; the brominated aliphatic chains include bromooctane; Specifically, the surface of the diatomaceous earth anti-icing agent is first modified using the silane coupling agent KH570 to introduce polymerizable double bonds. Then, methyl acrylate and unsaturated quaternary ammonium salts are polymerized in situ on the surface of the diatomaceous earth anti-icing agent, forming a chemically bonded organic-inorganic composite anti-icing agent. During the rainy seasons of spring, summer, and autumn, the polymer coating maintains good flexibility and integrity, effectively sealing the internal anti-icing components and preventing them from being washed away by rainwater, thus solving the problem of easy failure of traditional materials. However, in winter, as the ambient temperature drops sharply, the movement of the methyl acrylate polymer chains is restricted, and the coating becomes brittle and hard, thus reducing stress and impact from vehicle traffic. Under these conditions, the coating layer is prone to micro-fracture or micro-cracks, thus precisely exposing the internal diatomaceous earth anti-icing agent and slowly releasing the anti-icing components. Meanwhile, the long aliphatic chains on the quaternary ammonium salt side chains in the polymer coating layer can significantly reduce the surface tension of water, hindering the spread of water molecules on the road surface and the nucleation of ice crystals, thus inhibiting icing from both physical and chemical dimensions. In addition, the benzophenone structural units in the coating layer, as endogenous ultraviolet absorbers, can effectively capture ultraviolet energy and convert it into heat energy dissipation, greatly improving the UV aging resistance of the acrylic composite anti-icing coating and ensuring the long-term stability and high-efficiency anti-icing ability of the coating in complex outdoor environments.

[0021] (3) The acrylic composite anti-icing coating of the present invention has excellent construction performance, supports a variety of construction methods, and dries quickly, enabling it to be put into use quickly, thereby significantly shortening the maintenance cycle and minimizing the interference with road traffic. Attached Figure Description

[0022] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein... Figure 1 Comparison of the anti-icing effect of the acrylic composite anti-icing coating of one embodiment of the present invention at -10°C.

[0023] Figure 2 This is a comparison of the de-icing effect of the specimens without the acrylic composite anti-icing coating of the present invention at -10℃.

[0024] The labels in the attached figures are as follows: 1 represents a specimen of acrylic composite anti-icing coating with a coating weight of 3%, 1-1 represents a specimen of acrylic composite anti-icing coating with a coating weight of 4%, and 1-2 represents a specimen of acrylic composite anti-icing coating with a coating weight of 6%. Detailed Implementation

[0025] To better understand the above technical solutions, the following will provide a detailed explanation of the technical solutions in conjunction with the accompanying drawings and specific implementation methods.

[0026] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0027] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0028] Those skilled in the art will understand the specific meaning of the above terms in this invention based on the specific circumstances. The invention will be further described below with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solutions of the invention and should not be construed as limiting the scope of protection of the invention.

[0029] The concentration of concentrated hydrochloric acid is 36-38%. The polymerization inhibitor used is 2,6-di-tert-butyl-p-methylphenol.

[0030] The brominated aliphatic chain uses 1-bromooctane.

[0031] The dispersant used is BYK-190.

[0032] The defoamer used is BYK-011.

[0033] The thickener used is BYK-410.

[0034] Example 1 A method for preparing an acrylic composite anti-icing coating, comprising the following steps: (1) Weigh and prepare each raw material component, and dry the nano titanium dioxide and nano silica at 120℃ for 3h; the raw material components include 30kg acrylic resin, 20kg composite anti-gelling agent, 3kg nano titanium dioxide, 2kg nano silica, 1kg dispersant, 0.5kg defoamer, 0.5kg thickener, and 33kg ethyl acetate; (2) Add ethyl acetate to the reactor, and add acrylic resin, composite anti-icing agent, nano titanium dioxide, nano silica, dispersant, defoamer and thickener in sequence under stirring at 300 r / min, and stir for 60 min; (3) Transfer the mixed material from step (2) to an ultrasonic dispersion device and ultrasonically disperse it for 2 hours at a power of 200W; (4) The material after ultrasonic dispersion in step (3) is filtered through a 200-mesh filter to obtain an acrylic composite anti-icing coating.

[0035] The preparation steps of the composite anti-icing agent are as follows: First, mix 5 parts by mass of KH-570 with 0.7 parts by mass of concentrated hydrochloric acid, stir and heat to 70°C, then add 4 parts by mass of deionized water dropwise over 30 minutes, and react at a constant temperature for 130 minutes after the addition is complete; then add 86 parts by mass of toluene, heat to boiling and distill at 105°C to remove alcohol, water and hydrochloric acid from the solution; heat to 110°C, add 4.6 parts by mass of diatomaceous earth anti-icing agent, and react under constant temperature and stirring under reflux for 6 hours; then add 0.07 parts by mass of initiator benzoyl peroxide, and slowly add 2.3 parts by mass of methyl acrylate and 3.8 parts by mass of unsaturated quaternary ammonium salt over 30 minutes, and continue the reaction for 3 hours; finally, filter, dry and grind through a 150-mesh sieve to obtain the composite anti-icing agent.

[0036] The preparation method of diatomaceous earth anti-coagulation agent is as follows: Anhydrous ethanol, emulsifier OP-10 and diatomaceous earth are mixed at a mass ratio of 78:1:2.2 and ultrasonically dispersed for at least 30 minutes to obtain a diatomaceous earth ethanol suspension; a saturated potassium chloride aqueous solution is heated to 58℃ and hydrochloric acid solution is added dropwise to adjust the pH to 1, and then added dropwise to the diatomaceous earth ethanol suspension at a volume ratio of 4:1 under ultrasonic oscillation to form a precipitate, which is then filtered, dried, ground and dried for later use to obtain the diatomaceous earth anti-coagulation agent.

[0037] The preparation method of the unsaturated quaternary ammonium salt is as follows: Under nitrogen protection, N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, and acetone are mixed and stirred for 30 min. Then, 5-chloro-2-hydroxybenzophenone is added, and the mixture is heated, stirred, refluxed, and cooled for 11 h. After removing excess potassium carbonate with hydrochloric acid, the mixture is extracted with diethyl ether, separated, and dried to remove acetone. Then, brominated aliphatic chains are added, and the temperature is raised to 110 °C. The mixture is heated, stirred, refluxed, and cooled for 4 h to obtain the unsaturated quaternary ammonium salt. The molar ratio of N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, 5-chloro-2-hydroxybenzophenone, and brominated aliphatic chains is 5:0.0005:6:5:6. The mass ratio of N,N-diallylethanolamine to acetone is 1:6.

[0038] Example 2 A method for preparing an acrylic composite anti-icing coating, comprising the following steps: (1) Weigh and prepare each raw material component, and dry the nano titanium dioxide and nano silica at 100℃ for 3h; the raw material components include 25kg acrylic resin, 25kg composite anti-icing agent, 4kg nano titanium dioxide, 3kg nano silica, 1.2kg dispersant, 0.6kg defoamer, 0.7kg thickener, and 40.5kg ethyl acetate; (2) Add ethyl acetate to the reactor, and add acrylic resin, composite anti-icing agent, nano titanium dioxide, nano silica, dispersant, defoamer and thickener in sequence under stirring at 400 r / min, and stir for 45 min; (3) Transfer the mixed material from step (2) to an ultrasonic dispersion device and ultrasonically disperse it for 1.5 hours at a power of 300W; (4) The material after ultrasonic dispersion in step (3) is filtered through a 200-mesh filter to obtain an acrylic composite anti-icing coating.

[0039] The preparation steps of the composite anti-icing agent are as follows: First, mix 5.5 parts by mass of KH-570 with 0.75 parts by mass of concentrated hydrochloric acid, stir and heat to 75°C, then add 4.5 parts by mass of deionized water dropwise over 30 minutes, and react at a constant temperature for 120 minutes after the addition is complete; then add 88 parts by mass of toluene, heat to boiling and distill at 105°C to remove alcohol, water and hydrochloric acid from the solution; heat to 120°C, add 5 parts by mass of diatomaceous earth anti-icing agent, and react under constant temperature and stirring under reflux for 5 hours; then add 0.075 parts by mass of initiator benzoyl peroxide, and slowly add 2.35 parts by mass of methyl acrylate and 3.4 parts by mass of unsaturated quaternary ammonium salt over 30 minutes, and continue the reaction for 3.5 hours; finally, filter, dry and grind through a 150-mesh sieve to obtain the composite anti-icing agent.

[0040] The preparation method of diatomaceous earth anti-coagulation agent is as follows: Anhydrous ethanol, emulsifier OP-10 and diatomaceous earth are mixed at a mass ratio of 79:1:2.3 and ultrasonically dispersed for at least 30 minutes to obtain a diatomaceous earth ethanol suspension; a saturated potassium chloride aqueous solution is heated to 60℃ and hydrochloric acid solution is added dropwise to adjust the pH to 1, and then added dropwise to the diatomaceous earth ethanol suspension at a volume ratio of 4:1 under ultrasonic oscillation to form a precipitate, which is then filtered, dried, ground and dried for later use to obtain the diatomaceous earth anti-coagulation agent.

[0041] The preparation method of the unsaturated quaternary ammonium salt is as follows: Under nitrogen protection, N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, and acetone are mixed and stirred for 45 min. Then, 5-chloro-2-hydroxybenzophenone is added, and the mixture is heated, stirred, refluxed, and cooled for 12 h. Excess potassium carbonate is removed with hydrochloric acid, and the mixture is extracted with diethyl ether, separated, and dried to remove acetone. Then, brominated aliphatic chains are added, the temperature is raised to 120 °C, and the mixture is heated, stirred, refluxed, and cooled for 3.5 h to obtain the unsaturated quaternary ammonium salt. The molar ratio of N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, 5-chloro-2-hydroxybenzophenone, and brominated aliphatic chains is 5:0.0008:6.5:8:7. The mass ratio of N,N-diallylethanolamine to acetone is 1:9.

[0042] Example 3 A method for preparing an acrylic composite anti-icing coating, comprising the following steps: (1) Weigh and prepare each raw material component, and dry the nano titanium dioxide and nano silica at 120℃ for 2h; the raw material components include 28kg acrylic resin, 22kg composite anti-icing agent, 4kg nano titanium dioxide, 3kg nano silica, 1.2kg dispersant, 0.6kg defoamer, 0.7kg thickener, and 40.5kg ethyl acetate; (2) Add ethyl acetate to the reactor, and add acrylic resin, composite anti-icing agent, nano titanium dioxide, nano silica, dispersant, defoamer and thickener in sequence under stirring at 500 r / min, and stir for 30 min; (3) Transfer the material mixed in step (2) to an ultrasonic dispersion device and ultrasonically disperse it for 1 hour at a power of 400W; (4) The material after ultrasonic dispersion in step (3) is filtered through a 300-mesh filter to obtain an acrylic composite anti-icing coating.

[0043] The preparation steps of the composite anti-icing agent are as follows: First, mix 6 parts by mass of KH-570 with 0.8 parts by mass of concentrated hydrochloric acid, stir and heat to 85°C, then add 5 parts by mass of deionized water dropwise over 30 minutes, and react at a constant temperature for 130 minutes after the addition is complete; then add 90 parts by mass of toluene, heat to boiling and distill at 105°C to remove alcohol, water and hydrochloric acid from the solution; heat to 120°C, add 5.5 parts by mass of diatomaceous earth anti-icing agent, and react under constant temperature and stirring under reflux for 6 hours; then add 0.07 parts by mass of initiator benzoyl peroxide, and slowly add 2.4 parts by mass of methyl acrylate and 2.9 parts by mass of unsaturated quaternary ammonium salt over 30 minutes, and continue the reaction for 4 hours; finally, filter, dry and grind through a 150-mesh sieve to obtain the composite anti-icing agent.

[0044] The preparation method of diatomaceous earth anti-coagulation agent is as follows: Anhydrous ethanol, emulsifier OP-10 and diatomaceous earth are mixed at a mass ratio of 80:1:2.4 and ultrasonically dispersed for at least 30 minutes to obtain a diatomaceous earth ethanol suspension; a saturated potassium chloride aqueous solution is heated to 62℃ and hydrochloric acid solution is added dropwise to adjust the pH to 1, and then added dropwise to the diatomaceous earth ethanol suspension at a volume ratio of 4:1 under ultrasonic oscillation to form a precipitate, which is then filtered, dried, ground and dried for later use to obtain the diatomaceous earth anti-coagulation agent.

[0045] The preparation method of the unsaturated quaternary ammonium salt is as follows: Under nitrogen protection, N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, and acetone are mixed and stirred for 60 min. Then, 5-chloro-2-hydroxybenzophenone is added, and the mixture is heated, stirred, refluxed, and cooled for 13 h. After removing excess potassium carbonate with hydrochloric acid, the mixture is extracted with diethyl ether, separated, and dried to remove acetone. Then, brominated aliphatic chains are added, the temperature is raised to 120 °C, and the mixture is heated, stirred, refluxed, and cooled for 4 h to obtain the unsaturated quaternary ammonium salt. The molar ratio of N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, 5-chloro-2-hydroxybenzophenone, and brominated aliphatic chains is 5:0.001:7:10:8. The mass ratio of N,N-diallylethanolamine to acetone is 1:12.

[0046] Comparative Example 1 The only difference between Comparative Example 1 and Example 2 is that the raw material components include: 25 kg of acrylic resin, 25 kg of diatomaceous earth, 4 kg of nano titanium dioxide, 3 kg of nano silica, 1.2 kg of dispersant, 0.6 kg of defoamer, 0.7 kg of thickener, and 40.5 kg of ethyl acetate.

[0047] Comparative Example 2 The only difference between Comparative Example 2 and Example 2 is that the raw material components include: 25 kg of acrylic resin, 25 kg of composite anti-icing agent, 1.2 kg of dispersant, 0.6 kg of defoamer, 0.7 kg of thickener, and 40.5 kg of ethyl acetate.

[0048] Comparative Example 3 The only difference between Comparative Example 3 and Example 2 is that the raw material components include: 25 kg of acrylic resin, 25 kg of diatomaceous earth anti-icing agent, 4 kg of nano titanium dioxide, 3 kg of nano silica, 1.2 kg of dispersant, 0.6 kg of defoamer, 0.7 kg of thickener, and 40.5 kg of ethyl acetate.

[0049] Comparative Example 4 The only difference between Comparative Example 4 and Example 2 is that the raw material components include: 25 kg of acrylic resin, 25 kg of diatomaceous earth anti-icing agent, 8 kg of octyldecyl dimethyl ammonium chloride, 4 kg of nano titanium dioxide, 3 kg of nano silica, 1.2 kg of dispersant, 0.6 kg of defoamer, 0.7 kg of thickener, and 40.5 kg of ethyl acetate.

[0050] Comparative Examples 5-9 The only difference between Comparative Examples 5-9 and Example 2 is that the mass ratio of methyl acrylate to unsaturated quaternary ammonium salt in the methyl acrylate polymer is 2.35:0, 2.35:2.7, 2.35:2.8, 2.35:3.9, and 2.35:4, respectively.

[0051] Example of effect Anti-icing performance test: The acrylic composite anti-icing coatings of the examples and comparative examples with a thickness of 0.4 mm were coated on asphalt pavement test specimens and allowed to dry naturally at room temperature. 10 μL of deionized water was dropped onto the surface of the coating specimen with a thickness of 0.4 mm, and the time it took for the water droplet to freeze completely was recorded in an environment of -10℃ and 60% relative humidity.

[0052] Abrasion resistance: Asphalt pavement test specimens coated with the acrylic composite anti-icing coatings of the examples and comparative examples were subjected to 500 simulated vehicle rolling tests. The results were recorded to determine whether there was significant wear on the coating surface and the retention rate of anti-icing performance.

[0053] Weather resistance: Asphalt pavement test specimens coated with the acrylic composite anti-icing coatings of the examples and comparative examples were subjected to a 1000-hour accelerated aging test and a 1000-hour ultraviolet aging test to test the retention rate of anti-icing performance. The anti-icing performance retention rate = 100%. Time for water droplets to freeze after aging / Time for water droplets to freeze before aging.

[0054] Table 1 Depend on Figures 1-2 As shown in Table 1, the acrylic composite anti-icing coatings prepared in Examples 1-3 have good anti-icing properties, wear resistance, and weather resistance. The anti-icing properties are better with increasing coating amount, while the surface of the asphalt pavement test specimens without acrylic composite anti-icing coating is completely covered by ice.

[0055] Comparative Example 1 used conventional diatomaceous earth instead of the composite anti-icing agent, Comparative Example 3 used only uncoated diatomaceous earth anti-icing agent, and Comparative Example 4 used a physical compound of diatomaceous earth anti-icing agent and octyldecyl dimethyl ammonium chloride. The test results showed that the coatings prepared in the above three comparative examples had weaker anti-icing performance than those in Example 2, and also had poorer wear resistance and weather resistance. This comparison not only confirmed that the compound of diatomaceous earth anti-icing agent and octyldecyl dimethyl ammonium chloride can effectively improve the performance of coatings, but also highlighted the superior advantages of the composite anti-icing agent used in this invention in terms of comprehensive performance in anti-icing, wear resistance and weather resistance.

[0056] Comparative Example 2, which did not include nano-titanium dioxide or nano-silica in its raw material components, produced an acrylic composite anti-icing coating with weaker anti-icing properties than Example 2. Furthermore, its abrasion resistance and weather resistance were significantly weaker than those of Example 2. This verifies that adding nano-titanium dioxide and nano-silica can improve the strength, abrasion resistance, and anti-aging properties of the coating.

[0057] Comparative Examples 5 to 9 investigated the effects of the mass ratio of methyl acrylate to unsaturated quaternary ammonium salt in the methyl acrylate polymer on performance at ratios of 2.35:0, 2.35:2.7, 2.35:2.8, 2.35:3.9, and 2.35:4. The results showed that with the increase of the amount of unsaturated quaternary ammonium salt, the anti-icing property of the coating first increased and then tended to stabilize, while the weather resistance continued to improve. When the mass ratio of methyl acrylate to unsaturated quaternary ammonium salt was controlled within the range of 2.35:(2.9~3.8), the composite anti-icing agent prepared by in-situ polymerization and encapsulation could effectively improve the anti-icing property, abrasion resistance, and weather resistance of the acrylic composite anti-icing coating.

[0058] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An acrylic composite anti-icing coating, characterized in that, The raw material components include 20%~35% acrylic resin, 15%~25% composite anti-icing agent, 1%~5% nano titanium dioxide, 2%~3% nano silica, 1%~5% additives, and 30%~50% environmentally friendly solvent.

2. The acrylic composite anti-icing coating according to claim 1, characterized in that, The composite anti-coating agent is obtained by coating diatomaceous earth anti-coating agent with methyl acrylate polymer; the diatomaceous earth anti-coating agent is obtained by combining diatomaceous earth with chloride salt.

3. The acrylic composite anti-icing coating according to claim 2, characterized in that, The methyl acrylate polymer is obtained by polymerizing methyl acrylate with an unsaturated quaternary ammonium salt.

4. The acrylic composite anti-icing coating according to claim 3, characterized in that, The unsaturated quaternary ammonium salt is obtained by reacting 5-chloro-2-hydroxybenzophenone with N,N-diallylethanolamine and then reacting it with a brominated aliphatic chain.

5. A method for preparing an acrylic composite anti-icing coating as described in any one of claims 1 to 4, characterized in that, step... include: (1) Weigh and prepare each raw material component, and dry the nano titanium dioxide and nano silicon dioxide; (2) Add environmentally friendly solvent to the reactor, and add acrylic resin, composite anti-icing agent, nano titanium dioxide, nano silica and additives in sequence under stirring conditions, and stir for 30~60min; (3) Transfer the mixed material from step (2) to an ultrasonic dispersion device and ultrasonically disperse for 1-2 hours; (4) Filter the material after ultrasonic dispersion in step (3) to obtain acrylic composite anti-icing coating.

6. The method for preparing the acrylic composite anti-icing coating according to claim 5, characterized in that, The preparation steps of the composite anti-icing agent are as follows: First, mix 5-6 parts by weight of KH-570 with 0.7-0.8 parts by weight of concentrated hydrochloric acid, stir and heat to 70-85°C, then add 4-5 parts by weight of deionized water dropwise over 30 minutes, and react at a constant temperature for 110-130 minutes after the addition is complete; then add 86-90 parts by weight of toluene, heat to boiling and distill at 105°C to remove alcohol, water and hydrochloric acid from the solution; heat to 110-120°C, add 4.6-5.5 parts by weight of diatomaceous earth anti-icing agent, and react under constant temperature and stirring under reflux for 4-6 hours; then add 0.07-0.08 parts by weight of initiator benzoyl peroxide, and slowly add 2.3-2.4 parts by weight of methyl acrylate and 2.9-3.8 parts by weight of unsaturated quaternary ammonium salt over 30 minutes, and continue the reaction for 3-4 hours; finally, after filtration, drying and grinding, the composite anti-icing agent is obtained.

7. The method for preparing the acrylic composite anti-icing coating according to claim 6, characterized in that, The preparation method of the diatomaceous earth anti-coagulation agent is as follows: Anhydrous ethanol, emulsifier OP-10, and diatomaceous earth are mixed and ultrasonically dispersed at a mass ratio of (78~80):1:(2.2~2.4) for at least 30 minutes to obtain a diatomaceous earth ethanol suspension; a saturated potassium chloride aqueous solution is heated to 58~62℃ and hydrochloric acid solution is added dropwise to adjust the pH to 1. Then, under ultrasonic oscillation, it is added dropwise to the diatomaceous earth ethanol suspension at a volume ratio of 4:1 to form a precipitate. Then, it is filtered, dried, ground, and dried again for later use to obtain the diatomaceous earth anti-coagulation agent.

8. The method for preparing the acrylic composite anti-icing coating according to claim 6, characterized in that, The preparation method of the unsaturated quaternary ammonium salt is as follows: Under nitrogen protection, N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, and acetone are mixed and stirred for 30-60 min. Then, 5-chloro-2-hydroxybenzophenone is added, and the mixture is heated, stirred, refluxed, and cooled for 11-13 h. After removing excess potassium carbonate and acetone, brominated aliphatic chains are added and the temperature is raised to 110-120 °C. The mixture is then heated, stirred, refluxed, and cooled for 3-4 h to obtain the unsaturated quaternary ammonium salt.

9. The method for preparing the acrylic composite anti-icing coating according to claim 6, characterized in that, The molar ratio of N,N-diallylethanolamine, polymerization inhibitor, potassium carbonate, 5-chloro-2-hydroxybenzophenone, and brominated aliphatic chain is 5:(0.0005~0.001):(6~7):(5~10):(6~8); the mass ratio of N,N-diallylethanolamine to acetone is 1:(6~12).

10. The application of an acrylic composite anti-icing coating as described in any one of claims 1 to 4, characterized in that, The acrylic composite anti-icing coating is used in the field of road anti-icing.

Images