Composite energy storage type pavement anti-icing self-repairing coating and preparation method and application thereof

Abstract

This disclosure provides a composite energy storage type anti-icing self-healing coating for road surfaces, its preparation method, and its application. The composite energy storage type anti-icing self-healing coating comprises, from top to bottom, a hydrophobic and wear-resistant surface layer, an energy storage and anti-icing intermediate layer, and an adhesive self-healing bottom layer. The hydrophobic and wear-resistant surface layer contains fluorinated siloxane oligomers with a surface energy less than or equal to 22 mN / m. The energy storage and anti-icing intermediate layer contains composite energy storage phase change microcapsules with a phase change temperature of -2 to 2℃. Furthermore, the adhesive self-healing bottom layer includes polycaprolactone microcapsules, which can rupture and release a self-healing core material capable of automatically bonding and repairing the microcracks when microcracks occur in the road surface.

Description

Technical Field

[0001] This invention belongs to the technical field of road engineering pavement maintenance materials, specifically relating to a composite energy storage type anti-icing self-healing coating for pavement, its preparation method, and its application. Background Technology

[0002] Existing anti-icing coatings for road surfaces are mainly classified into three types: superhydrophobic, slow-release salt-melting, and microwave-heated. Superhydrophobic coatings rely on low surface energy materials to construct micro-nano structures, which are prone to failure due to wheel wear and have a short anti-icing effect. Slow-release salt-melting coatings mostly use inorganic salts, which have problems such as salt precipitation pollution, road surface corrosion, and uneven release. Microwave-heated coatings require supporting heating equipment, have high energy consumption, and are prone to damaging the asphalt base layer.

[0003] In addition, existing coatings generally lack self-healing capabilities. Micro-cracks and wear potholes on the road surface will accelerate coating failure, making it difficult to achieve the triple performance of anti-icing, wear resistance and self-healing. Long-term service stability in cold regions is also insufficient. Summary of the Invention

[0004] This invention aims to solve the technical problems of existing anti-icing coatings, such as poor wear resistance, short anti-icing time, snow melting salt pollution, lack of self-healing ability, high energy consumption of microwave heating, and damage to the base layer. It provides a composite energy storage type anti-icing self-healing coating for road surfaces, its preparation method, and its application. This composite energy storage type anti-icing self-healing coating for road surfaces has passive anti-icing, active energy storage and ice melting, and dynamic self-healing functions. It is suitable for complex working conditions in cold regions, extends the service life of the coating, reduces maintenance costs, and achieves environmentally friendly and efficient anti-icing.

[0005] To achieve the above objectives, the present invention employs the following technical solution: The first aspect of this disclosure provides a composite energy storage type anti-icing self-healing coating for road surfaces, comprising a hydrophobic and wear-resistant top layer, an energy storage and anti-icing intermediate layer, and an adhesive self-healing bottom layer arranged sequentially from top to bottom. The hydrophobic and wear-resistant surface layer comprises fluorinated siloxane oligomers with a surface energy of less than or equal to 22 mN / m. The energy storage and anti-condensation intermediate layer comprises composite energy storage phase change microcapsules with a phase change temperature of -2 to 2°C, and The self-healing adhesive base layer includes polycaprolactone microcapsules, which can rupture and release a self-healing core material that can automatically bond and repair the microcracks when microcracks occur in the road surface.

[0006] In some implementations, the total thickness of the composite energy storage type anti-icing self-healing coating is 2.8~3.7mm, wherein the thickness of the hydrophobic wear-resistant surface layer is 0.8~1.2mm, the thickness of the energy storage anti-icing intermediate layer is 1.2~1.5mm, and the thickness of the adhesive self-healing underlayer is 0.8~1.0mm.

[0007] In some embodiments, the interfacial bonding strength between the hydrophobic wear-resistant surface layer, the energy storage anti-icing intermediate layer, and the adhesive self-healing bottom layer is greater than or equal to 3.2 MPa, the interlayer penetration crosslinking depth is 0.1~0.2 mm, and the overall porosity of the composite energy storage type pavement anti-icing self-healing coating is less than or equal to 8%.

[0008] In some embodiments, the topcoat composition forming the hydrophobic and abrasion-resistant surface layer comprises, by weight: 30-38 parts of fluorinated modified siloxane oligomers, 7-10 parts of hydrophobically modified nano zinc oxide, 4-6 parts of basalt short fibers, 5-8 parts of polytetrafluoroethylene micro powder, 0.5 to 1 part silicone leveling agent, and 15-20 parts deionized water.

[0009] In some embodiments, the fluorinated siloxane oligomer has a solid content of 55-60%, a fluorine content of 12-15%, and a viscosity of 400-500 mPa·s.

[0010] In some embodiments, the hydrophobically modified nano zinc oxide has a particle size of 30-50 nm, and the hydrophobically modified nano zinc oxide is nano zinc oxide that has been hydrophobically modified with γ-aminopropyltriethoxysilane.

[0011] In some embodiments, the polytetrafluoroethylene micropowder has a particle size of 2-5 μm and a coefficient of friction of less than or equal to 0.12.

[0012] In some embodiments, the intermediate layer coating composition forming the energy storage anti-condensation intermediate layer comprises, by weight parts: 35-42 parts modified acrylic emulsion, 22-28 composite energy storage phase change microcapsules, 10-14 parts of slow-release organic de-icing agent, 5-7 parts carbon aerogel particles, 0.8~1.2 parts of water-based defoamer, and 1-2 parts hydroxyethyl cellulose.

[0013] In some embodiments, the modified acrylic emulsion has a solid content of 48-52%, a glass transition temperature of -5 to 0°C, and a viscosity of 600-800 mPa·s.

[0014] In some embodiments, the particle size of the composite energy storage phase change microcapsules is 80~120 μm.

[0015] In some embodiments, the capsule wall of the composite energy storage phase change microcapsule is melamine-formaldehyde resin, and the core material of the composite energy storage phase change microcapsule is an octadecane-stearic acid composite phase change material with a mass ratio of (75~85):(15~25).

[0016] In some embodiments, the latent heat of phase change of the composite energy storage phase change microcapsule is 180~210 J / g and the composite energy storage phase change microcapsule is thermally stable below 120°C.

[0017] In some embodiments, the slow-release organic de-icing agent is a compound mixture of ethylene glycol monomethyl ether and sodium citrate in a mass ratio of (40~50):(50~60), and the slow-release organic de-icing agent has a slow-release period of greater than or equal to 180 days and a freezing point reduction of 12~15°C.

[0018] In some embodiments, the carbon aerogel particles have a particle size of 50-80 μm, a porosity of 85-90%, a specific surface area of ​​600-700 m² / g, and a thermal conductivity of 0.025-0.03 W / (m·K).

[0019] In some embodiments, the undercoat composition forming the self-healing adhesive underlayer comprises, by weight: 45-55 parts of epoxy-modified polyurethane component A, 20-28 parts of epoxy-modified polyurethane component B, 6-9 parts nano-silica, 8-12 parts of polycaprolactone microcapsules, 1.5~2.5 parts silane coupling agent, 3-5 parts of fumed silica, and 2-3 parts dioctyl phthalate.

[0020] In some embodiments, the epoxy-modified polyurethane component A is an epoxy-modified polyurethane prepolymer with an epoxy value of 0.22 to 0.26 eq / 100g and a viscosity of 2,500 to 3,000 mPa·s.

[0021] In some embodiments, the epoxy-modified polyurethane component B is an aliphatic amine curing agent with an amine value of 380-420 mgKOH / g and a viscosity of 800-1,000 mPa·s.

[0022] In some embodiments, the polycaprolactone microcapsules have a particle size of 100-150 μm.

[0023] In some embodiments, the capsule wall of the polycaprolactone microcapsules comprises sodium alginate.

[0024] In some embodiments, the core material of the polycaprolactone microcapsules is a polyurethane prepolymer with a solid content of 45-50%.

[0025] In some embodiments, the strength of the polycaprolactone microcapsules is greater than or equal to 0.8 MPa.

[0026] In some embodiments, the fumed silica has a particle size of 10-20 nm and a specific surface area of ​​300-350 m². 2 / g.

[0027] The second aspect of this disclosure provides a method for preparing a composite energy storage type anti-icing self-healing coating for road surfaces as described in the first aspect, comprising: S1. Prepare the primer coating composition; S2. Prepare the intermediate layer coating composition; S3, preparing a topcoat composition; and S4. The base coat composition, the intermediate coat composition and the top coat composition are sequentially sprayed onto the road surface and allowed to cure naturally for 24 hours to obtain the composite energy storage type anti-icing self-healing coating.

[0028] In some implementations, step S1 includes: S11. Under stirring conditions, add silane coupling agent and dioctyl phthalate to epoxy-modified polyurethane component A to obtain a mixture containing epoxy-modified polyurethane component A. S12. Under stirring conditions, nano-silica is added to the mixture containing epoxy-modified polyurethane component A in three portions, with an interval of 3 minutes between each addition, to obtain a mixture containing nano-silica. S13. Under stirring at 500 r / min, epoxy-modified polyurethane component B is slowly added to the mixture containing nano-silica for 8 minutes to obtain a crosslinked mixture; and S14. Polycaprolactone microcapsules are slowly added to the crosslinked mixture under stirring at 500 r / min for 5 minutes to obtain the underlying coating composition.

[0029] In some implementations, step S2 includes: S21. Add an aqueous defoamer and hydroxyethyl cellulose to the modified acrylic emulsion to obtain a bubble-free mixed emulsion. S22. Carbon aerogel particles are added to the bubble-free mixed emulsion in two separate additions, with a 2-minute interval between each addition, to obtain a mixed emulsion containing carbon aerogel particles. S23. Composite energy storage phase change microcapsules are added to the mixed emulsion containing carbon aerogel particles under stirring at 500 r / min to obtain a mixed emulsion containing the composite energy storage phase change microcapsules; and S24. Add a slow-release organic de-icing agent to the mixed emulsion containing the composite energy storage phase change microcapsules while stirring at 400 r / min to obtain the intermediate layer coating composition.

[0030] In some implementations, step S3 includes: S31. Add organosilicon leveling agent and deionized water to fluorinated siloxane oligomers to obtain fluorinated siloxane oligomer solution. S32. A mixture of hydrophobically modified nano-zinc oxide and polytetrafluoroethylene micropowder is added to the fluorinated siloxane oligomer solution in three separate additions, with a 4-minute interval between each addition, to obtain a solution containing the powder; and S33. Basalt short fibers are added to the powder-containing solution under stirring at 600 r / min to obtain the surface coating composition.

[0031] A third aspect of this disclosure provides a cement / asphalt concrete pavement, wherein the cement / asphalt concrete pavement is covered with a composite energy storage type anti-icing self-healing coating, the composite energy storage type anti-icing self-healing coating being a composite energy storage type anti-icing self-healing coating prepared according to the method described in the first aspect or according to the method described in the second aspect.

[0032] Compared with the prior art, the present invention has the following beneficial effects: (1) In the self-healing adhesive layer of the composite energy storage type road anti-icing self-healing coating disclosed herein, the polycaprolactone microcapsules can be uniformly dispersed in the cross-linked network formed by the matrix resin. As the self-healing core, when micro-cracks occur on the road surface, the microcapsules rupture to release the core material and automatically bond and repair the cracks.

[0033] (2) In the energy storage and anti-icing intermediate layer of the composite energy storage type pavement anti-icing self-healing coating disclosed herein, modified acrylic emulsion is cured to form an elastic matrix, composite energy storage phase change microcapsules and carbon aerogel particles are uniformly dispersed in the matrix, and slow-release organic de-icing agent is dissolved in the matrix and slowly released at low temperature to lower the freezing point. In addition, carbon aerogel further improves the heat conduction efficiency and accelerates the release of latent heat of phase change material.

[0034] (3) In the hydrophobic and wear-resistant surface layer of the composite energy storage type anti-icing self-healing coating for road surfaces disclosed herein, fluorine-modified siloxane is cured to form a low surface energy film, and polytetrafluoroethylene micropowder and hydrophobic nano zinc oxide are uniformly dispersed to construct a superhydrophobic micro-rough structure. In addition, basalt short fibers penetrate the surface layer to form a skeleton structure, which greatly improves wear resistance and impact resistance. Furthermore, the surface layer and the intermediate layer are cross-linked through siloxane to form a stable interface.

[0035] (4) The composite energy storage type anti-icing self-healing coating of the present invention can achieve weather resistance ≥ 5 years, excellent waterproof and seepage-proof and anti-skid performance, and can meet the long-term anti-icing, wear-resistant and self-healing requirements of asphalt and cement concrete pavement in cold regions. It has strong practicality and engineering adaptability. Detailed Implementation

[0036] To enable those skilled in the art to better understand the present disclosure, the technical solutions in the embodiments of the present disclosure are clearly and completely described. Obviously, the described embodiments are only some embodiments of the present disclosure, and not all embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by those of ordinary skill in the art without creative effort should fall within the scope of protection of the present disclosure.

[0038] When a range of values ​​is provided, it should be understood that, unless the context explicitly specifies otherwise, every intermediate value between the upper and lower limits of the range (to one-tenth of the lower limit unit), as well as any other specified or intermediate value within the specified range, is included in this disclosure. The upper and lower limits of these smaller ranges may be independently included within the smaller range and also within this disclosure, subject to any expressly excluded limits within the specified range. When a specified range includes one or two limits, the range excluding any one or both of these included limits is also included in this disclosure.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Although any methods and materials similar to or equivalent to those described herein may also be used in the practice or testing of this disclosure, preferred methods and materials are now described.

[0040] Upon reading this disclosure, it will be apparent to those skilled in the art that each individual embodiment described and illustrated herein has discrete components and features that can be readily separated from or combined from features of any other several embodiments without departing from the scope or spirit of this disclosure. Any of the described methods may be performed in the order of the events or in any other logically possible order.

[0041] Unless otherwise stated, embodiments of this disclosure will employ techniques from the fields of chemistry, organic chemistry, organometallic chemistry, physics, petrochemistry, and engineering mechanics, which are within the skill level of those skilled in the art. These techniques are well explained in the literature.

[0042] The following examples are provided to demonstrate to those skilled in the art how to perform the disclosed and claimed methods and how to use the disclosed and claimed compositions and compounds in accordance with the full disclosure and description. Efforts have been made to ensure the accuracy of figures (e.g., quantities, temperatures, etc.), but some errors and deviations should be taken into account.

[0043] Existing anti-icing coatings for road surfaces are mainly classified into three types: superhydrophobic, slow-release salt-melting, and microwave-heated. Superhydrophobic coatings rely on low surface energy materials to construct micro-nano structures, which are prone to failure due to wheel wear and have a short anti-icing effect. Slow-release salt-melting coatings mostly use inorganic salts, which have problems such as salt precipitation pollution, road surface corrosion, and uneven release. Microwave-heated coatings require supporting heating equipment, have high energy consumption, and are prone to damaging the asphalt base layer.

[0044] In addition, existing coatings generally lack self-healing capabilities. Micro-cracks and wear potholes on the road surface will accelerate coating failure, making it difficult to achieve the triple performance of anti-icing, wear resistance and self-healing. Long-term service stability in cold regions is also insufficient.

[0045] To address the shortcomings of existing technologies, this disclosure provides a composite energy-storage type anti-icing self-healing coating for road surfaces, comprising a hydrophobic and wear-resistant top layer, an energy-storage and anti-icing intermediate layer, and a bonding and self-healing bottom layer arranged sequentially from top to bottom. The three layers exhibit a gradient functional distribution, and are cross-linked through chemical bonds to form a unified structure, eliminating the risk of delamination and peeling. The interfacial bonding strength between the hydrophobic and wear-resistant top layer, the energy-storage and anti-icing intermediate layer, and the bonding and self-healing bottom layer is greater than or equal to 3.2 MPa, and the interlayer penetration and cross-linking depth is 0.1~0.2 mm, thus preventing interfacial delamination. Furthermore, the overall porosity of the composite energy-storage type anti-icing self-healing coating is less than or equal to 8%, exhibiting excellent waterproof and impermeable performance, effectively preventing moisture from penetrating into the road base layer.

[0046] For the hydrophobic and wear-resistant surface layer, it comprises a fluorinated modified siloxane oligomer with a surface energy less than or equal to 22 mN / m. In some embodiments, the surface coating composition forming the hydrophobic and wear-resistant surface layer comprises, by weight, 30-38 parts of fluorinated modified siloxane oligomer, 7-10 parts of hydrophobic modified nano-zinc oxide, 4-6 parts of basalt short fibers, 5-8 parts of polytetrafluoroethylene micropowder, 0.5-1 part of organosilicon leveling agent, and 15-20 parts of deionized water.

[0047] In the topcoat composition, the solid content of the fluorinated siloxane oligomer is 55-60%, the fluorine content is 12-15%, and the viscosity is 400-500 mPa·s. The particle size of the hydrophobically modified nano-zinc oxide is 30-50 nm, and the hydrophobically modified nano-zinc oxide is nano-zinc oxide that has been hydrophobically modified by γ-aminopropyltriethoxysilane. The particle size of the polytetrafluoroethylene micropowder is 2-5 μm, and the coefficient of friction is less than or equal to 0.12.

[0048] In the hydrophobic and wear-resistant surface layer formed by the disclosed topcoat composition, fluorinated siloxane can form a low surface energy film through curing, and polytetrafluoroethylene micropowder and hydrophobic nano-zinc oxide can be uniformly dispersed in the fluorinated siloxane, thereby constructing a superhydrophobic micro-rough structure. Basalt short fibers run through the entire surface layer, forming a skeleton structure, which greatly improves wear resistance and impact resistance.

[0049] For the energy storage and anti-condensation intermediate layer, it comprises composite energy storage phase change microcapsules with a phase change temperature of -2 to 2°C. In some embodiments, the intermediate layer coating composition forming the energy storage and anti-condensation intermediate layer comprises, by weight, 35 to 42 parts of modified acrylic emulsion, 22 to 28 parts of composite energy storage phase change microcapsules, 10 to 14 parts of slow-release organic de-icing agent, 5 to 7 parts of carbon aerogel particles, 0.8 to 1.2 parts of aqueous defoamer, and 1 to 2 parts of hydroxyethyl cellulose.

[0050] In the intermediate coating composition, the modified acrylic emulsion has a solid content of 48-52%, a glass transition temperature of -5-0°C, and a viscosity of 600-800 mPa·s.

[0051] The composite energy storage phase change microcapsules of the intermediate layer coating composition include a capsule wall and a core material. The capsule wall is melamine-formaldehyde resin. The core material is an octadecane-stearic acid composite phase change material, wherein the mass ratio of octadecane to stearic acid is (75-85):(15-25). The composite energy storage phase change microcapsules have a particle size of 80-120 μm, a latent heat of phase change of 180-210 J / g, and are thermally stable below 120°C.

[0052] The intermediate coating composition further includes a slow-release organic de-icing agent. The slow-release organic de-icing agent is a compound mixture of ethylene glycol monomethyl ether and sodium citrate, wherein the mass ratio of ethylene glycol monomethyl ether to sodium citrate is (40~50):(50~60). The slow-release organic de-icing agent has a release period greater than or equal to 180 days and a freezing point depression of 12~15°C.

[0053] The intermediate coating composition further includes carbon aerogel particles. The carbon aerogel particles have a particle size of 50-80 μm, a porosity of 85-90%, and a specific surface area of ​​600-700 m². 2 / g, and the thermal conductivity is 0.025~0.03 W / (m·K).

[0054] Therefore, in the energy-storing and anti-condensation intermediate layer formed by the intermediate coating composition, the modified acrylic emulsion forms an elastic matrix through curing. Composite energy-storing phase change microcapsules and carbon aerogel particles are uniformly dispersed within the elastic matrix, while a slow-release organic de-icing agent dissolves within the elastic matrix. At low temperatures, the slow-release organic de-icing agent is slowly released, thereby lowering the freezing point. Furthermore, the carbon aerogel can improve thermal conductivity and accelerate the release of the latent heat of the phase change material.

[0055] For the self-healing adhesive undercoat, it includes polycaprolactone microcapsules, which rupture upon the formation of microcracks in the pavement, releasing a self-healing core material capable of automatically bonding and repairing the microcracks. In some embodiments, the undercoat composition forming the self-healing adhesive undercoat comprises, by weight, 45-55 parts of epoxy-modified polyurethane component A, 20-28 parts of epoxy-modified polyurethane component B, 6-9 parts of nano-silica, 8-12 parts of polycaprolactone microcapsules, 1.5-2.5 parts of silane coupling agent, 3-5 parts of fumed silica, and 2-3 parts of dioctyl phthalate.

[0056] The epoxy-modified polyurethane component A of the primer composition is an epoxy-modified polyurethane prepolymer with an epoxy value of 0.22-0.26 eq / 100g and a viscosity of 2,500-3,000 mPa·s. The epoxy-modified polyurethane component B of the primer composition is a fatty amine curing agent with an amine value of 380-420 mgKOH / g and a viscosity of 800-1,000 mPa·s.

[0057] The polycaprolactone microcapsules comprise a capsule wall and a core material. The capsule wall contains sodium alginate, and the core material is a polyurethane prepolymer with a solid content of 45-50%. The polycaprolactone microcapsules have a particle size of 100-150 μm and a strength greater than or equal to 0.8 MPa.

[0058] Furthermore, the fumed silica has a particle size of 10-20 nm and a specific surface area of ​​300-350 m². 2 / g.

[0059] In the self-healing adhesive undercoat formed by the primer composition, after the epoxy-modified polyurethane A component and epoxy-modified polyurethane B component are mixed, the epoxy groups of epoxy-modified polyurethane A component undergo a cross-linking reaction with the amine groups of epoxy-modified polyurethane B component, forming a dense three-dimensional network structure. Nano-silica and fumed silica fill the network pores of the dense three-dimensional network structure, improving the density of the self-healing adhesive undercoat. Furthermore, polycaprolactone microcapsules are also uniformly dispersed in the cross-linked network of the dense three-dimensional network structure, serving as the self-healing core. When microcracks occur in the road surface, the polycaprolactone microcapsules rupture and release the polyurethane prepolymer within, allowing the polyurethane prepolymer to automatically bond and repair the microcracks in the road surface through contact with moisture.

[0060] In some embodiments, the total thickness of the composite energy storage type pavement anti-icing self-healing coating is 2.8~3.7 mm, wherein the thickness of the hydrophobic wear-resistant surface layer is 0.8~1.2 mm, the thickness of the energy storage anti-icing intermediate layer is 1.2~1.5 mm, and the thickness of the adhesive self-healing underlayer is 0.8~1.0 mm. The hydrophobic wear-resistant surface layer and the energy storage anti-icing intermediate layer are cross-linked through siloxane to form a stable interface.

[0061] This disclosure also provides a method for preparing a composite energy storage type anti-icing self-healing coating for road surfaces, comprising: S1. Prepare the primer coating composition; S2. Prepare the intermediate layer coating composition; S3, preparing a topcoat composition; and S4. The base coat composition, the intermediate coat composition and the top coat composition are sequentially sprayed onto the road surface and allowed to cure naturally for 24 hours to obtain the composite energy storage type anti-icing self-healing coating.

[0062] For the preparation method of the base coat composition, step S1 includes: S11. Under stirring conditions, add silane coupling agent and dioctyl phthalate to epoxy-modified polyurethane component A to obtain a mixture containing epoxy-modified polyurethane component A. S12. Under stirring conditions, nano-silica is added to the mixture containing epoxy-modified polyurethane component A in three portions, with an interval of 3 minutes between each addition, to obtain a mixture containing nano-silica. S13. Under stirring at 500 r / min, epoxy-modified polyurethane component B is slowly added to the mixture containing nano-silica for 8 minutes to obtain a crosslinked mixture; and S14. Polycaprolactone microcapsules are slowly added to the crosslinked mixture under stirring at 500 r / min for 5 minutes to obtain the underlying coating composition.

[0063] For the method of preparing the intermediate layer composition, step S2 includes: S21. Add an aqueous defoamer and hydroxyethyl cellulose to the modified acrylic emulsion to obtain a bubble-free mixed emulsion. S22. Carbon aerogel particles are added to the bubble-free mixed emulsion in two separate additions, with a 2-minute interval between each addition, to obtain a mixed emulsion containing carbon aerogel particles. S23. Composite energy storage phase change microcapsules are added to the mixed emulsion containing carbon aerogel particles under stirring at 500 r / min to obtain a mixed emulsion containing the composite energy storage phase change microcapsules; and S24. Add a slow-release organic de-icing agent to the mixed emulsion containing the composite energy storage phase change microcapsules while stirring at 400 r / min to obtain the intermediate layer coating composition.

[0064] For the preparation method of the topcoat composition, step S3 includes: S31. Add organosilicon leveling agent and deionized water to fluorinated siloxane oligomers to obtain fluorinated siloxane oligomer solution. S32. A mixture of hydrophobically modified nano-zinc oxide and polytetrafluoroethylene micropowder is added to the fluorinated siloxane oligomer solution in three separate additions, with a 4-minute interval between each addition, to obtain a solution containing the powder; and S33. Basalt short fibers are added to the powder-containing solution under stirring at 600 r / min to obtain the surface coating composition.

[0065] The hydrophobic and wear-resistant surface layer prepared by the above method has a water contact angle ≥152°, a roll-off angle ≤6°, wear loss (500 cycles of rolling) ≤0.05 g / cm², and no powdering after 500 hours of UV aging. The energy storage and anti-condensation intermediate layer has a phase change temperature of -2~2℃, a latent heat of phase change ≥180 J / g, a slow-release period ≥180 days, and a freezing point ≤-12℃. The bonding strength of the self-healing adhesive underlayer is ≥3.2 MPa, the self-healing efficiency (micro-cracks) is ≥85%, and the shear strength is ≥2.8 MPa. The overall coating has a weather resistance ≥5 years, is resistant to salt spray (1000 hours) without corrosion, has a water permeability coefficient ≤0 mL / min, and an anti-slip value ≥48 BPN.

[0066] Therefore, the composite energy storage type anti-icing self-healing coating for road surfaces has the functions of passive anti-icing, active energy storage and ice melting, and dynamic self-healing. It is suitable for complex working conditions in cold regions, extends the service life of the coating, reduces maintenance costs, and achieves environmentally friendly and efficient anti-icing.

[0067] Therefore, this disclosure also provides a cement / asphalt concrete pavement, wherein the cement / asphalt concrete pavement is covered with a composite energy storage type anti-icing self-healing coating, the composite energy storage type anti-icing self-healing coating being the aforementioned composite energy storage type anti-icing self-healing coating or a composite energy storage type anti-icing self-healing coating prepared according to the aforementioned method.

[0068] To make the embodiments of this disclosure easier to understand, the present disclosure will be described in detail below with reference to the embodiments. These embodiments are for illustrative purposes only and are not limited to the application scope of this disclosure.

[0069] Unless otherwise specified, the specific operations and processing methods or conditions not described in the following embodiments are conventional methods in the art or are performed in accordance with the techniques or conditions described in the literature in the art or in accordance with the product manual.

[0070] Unless otherwise specified, all reagents or instruments used in the following examples that do not specify the manufacturer are commercially available products and conventional instruments in the field.

[0071] In the following examples, unless otherwise specified, all percentages are weight percentages.

[0072] The raw materials undergo pretreatment, as follows: Nano-silica and fumed silica were placed in a vacuum drying oven at a temperature of 110℃ and a vacuum of -0.08 to -0.1 MPa for 2.5 h. After drying, they were removed, cooled to room temperature in a desiccator, and sealed for storage to prevent secondary moisture absorption.

[0073] Polycaprolactone microcapsules are passed through a 120-mesh standard sieve to remove broken and clumped particles, retaining intact microcapsules. They are then stored at room temperature in a sealed, light-protected environment, and must not be squeezed or exposed to high temperatures.

[0074] Stir the epoxy-modified polyurethane component A and component B separately for 5 minutes (300 r / min) to remove precipitates, and set aside for later use.

[0075] Composite energy storage phase change microcapsules were passed through a 100-mesh standard sieve to remove broken particles; they were then placed in a sealed container and left to stand at room temperature for 24 hours to ensure the microcapsules remained stable and leak-free.

[0076] Carbon aerogel particles were added to deionized water and ultrasonically dispersed for 10 min (ultrasonic power 300 W) to remove surface dust; after filtration, they were dried at 60℃ for 1 h and cooled for later use.

[0077] The modified acrylic emulsion was stirred at 300 r / min for 5 min to remove surface bubbles and was then ready for use.

[0078] Hydrophobically modified nano zinc oxide is passed through a 200-mesh standard sieve to remove agglomerated particles and is ready for use.

[0079] The basalt short fibers are manually sorted to remove impurities, dried in an 80℃ drying oven for 30 minutes, and then loosened after cooling to prevent the fibers from tangling.

[0080] The fluorinated siloxane oligomer was stirred at 300 r / min for 5 min and set aside.

[0081] Other chemicals were not processed or purified.

[0082] The specific testing methods disclosed herein are as follows: The water contact angle was measured using a contact angle measuring instrument according to the droplet method / shape image analysis method in GB / T 30447-2013 "Method for Measurement of Contact Angle of Nanofilms". The measurements were taken under the following conditions: laboratory temperature (23±2)℃, relative humidity (50±10)%, test water conforming to GB / T 6682, droplet volume 5 μL, and droplet in contact with the coating surface for 60 s. At least 5 different locations were selected for measurement for each sample and the average value was taken.

[0083] The roll-off angle was measured using a contact angle measuring instrument equipped with an adjustable tilt stage, in accordance with the testing environment specified in GB / T 30447-2013 "Method for Measurement of Contact Angle of Nanofilms". The test was conducted under laboratory conditions of (23±2)℃, (50±10)% relative humidity, 10 μL droplet volume, and a tilt stage rise rate of 1° / s. The tilt angle at which the droplet begins to roll continuously or moves more than 2 mm was recorded as the roll-off angle. Each sample was tested at least 5 times and the average value was taken.

[0084] Abrasion loss was measured using a rotary rubber abrasive wheel abrasion tester according to GB / T 1768-2006 "Determination of Abrasion Resistance of Paints and Varnishes - Rotary Rubber Abrasive Wheel Method". A CS-10 rubber abrasive wheel was used, with a load of 1000 g and a rotation speed of 1000 r. The abrasion loss was calculated by dividing the difference in specimen mass before and after the test by the abrasion area, with units of g / cm². 2 .

[0085] UV aging resistance was tested according to GB / T 23987.3-2025 "Laboratory Light Source Exposure Methods for Paints and Varnishes Part 3: Fluorescent UV Lamp"; after 500 hours of cumulative exposure using a UVA-340 fluorescent UV lamp for irradiation / condensation cycle, chalking, discoloration, cracking and peeling were evaluated according to GB / T 1766-2008 "Rating Method for Aging of Paint and Varnish Coatings".

[0086] The phase transition temperature was tested according to JT / T 1210.1-2018 "De-icing and snow-melting materials for asphalt mixtures for highways - Part 1: Phase change materials" and in conjunction with GB / T 19466.3-2004 "Differential scanning calorimetry (DSC) for plastics - Part 3: Determination of melting and crystallization temperature and enthalpy". The DSC curve was measured using a differential scanning calorimeter under nitrogen atmosphere, sample mass of 5-10 mg, and heating and cooling rate of 5℃ / min. The peak phase transition temperature was taken as the phase transition temperature.

[0087] The latent heat of phase change was tested according to JT / T 1210.1-2018 "De-icing and snow-melting materials for asphalt mixtures for highways - Part 1: Phase change materials" and in conjunction with GB / T 19466.3-2004 "Differential scanning calorimetry (DSC) for plastics - Part 3: Determination of melting and crystallization temperature and enthalpy". The latent heat of phase change per unit mass of sample was obtained by integrating the phase change peak area of ​​the DSC curve, with the unit being J / g.

[0088] The controlled release period was tested according to the relevant requirements for the release performance and melting performance of melting materials in JT / T 1210.2-2018 "De-icing and snow-melting materials for highway asphalt mixtures - Part 2: Salt-based materials". The energy storage anti-condensation intermediate layer sample was placed in deionized water for periodic extraction. The freezing point of the extract and the 4-hour melting rate were measured periodically. When the freezing point of the extract decreased by less than 12℃ or the 4-hour melting rate decreased by less than 80% of the initial value, the controlled release was deemed to have failed. The cumulative number of extraction days before failure was recorded as the controlled release period.

[0089] Freezing point was tested according to GB / T 23851-2017 "De-icing Agents"; slow-release organic de-icing agents or energy-storing anti-condensation intermediate layer extracts were taken as samples, and their freezing temperature was measured using a freezing point measuring device. Each sample was tested in parallel for no less than 3 times and the average value was taken.

[0090] The bond strength was tested according to the test method for interlayer bond strength of emulsified asphalt in Appendix A of JT / T 1239-2019 "Technical Conditions for Anti-icing Coating Materials for Asphalt Pavement"; the specimen was kept in an environment of (25±2)℃ for more than 6 hours and then subjected to axial tension. The bond strength was obtained by dividing the maximum tensile load by the bond area.

[0091] The self-healing efficiency was tested according to GB / T 5210-2006 "Paints and Varnishes - Pull-off Adhesion Test". The initial pull-off bond strength of the coating and the pull-off bond strength after repair for 24 h under conditions of (25±2)℃ and (60±10)% relative humidity after artificial scratch were measured respectively. The self-healing efficiency was calculated as "pull-off bond strength after repair / initial pull-off bond strength × 100%".

[0092] Shear strength was tested according to GB / T 7124-2008 "Determination of tensile shear strength of adhesives (rigid material to rigid material)"; coating-base overlap specimens were prepared and subjected to tensile shear at a loading rate of 5 mm / min under (25±2)℃ conditions, and the shear strength was calculated by dividing the maximum failure load by the overlap area.

[0093] Weather resistance was tested according to GB / T 1865-2009 "Artificial climate aging and artificial radiation exposure of paints and varnishes with filtered xenon arc radiation". The coated specimens were subjected to artificial climate aging under xenon arc lamps, and appearance defects were evaluated according to GB / T 1766-2008. The weather resistance years were calculated based on the accelerated aging results that showed no chalking, no cracking, no peeling, and a key performance retention rate of not less than 80%.

[0094] Salt spray resistance was tested according to GB / T 10125-2021 "Salt spray test for corrosion in artificial atmosphere". Neutral salt spray conditions were used, with a sodium chloride solution mass fraction of 5% and a test chamber temperature of (35±2)℃. After continuous spraying for 1000 h, the coating was observed to see if corrosion, blistering, cracking or peeling occurred.

[0095] The permeability coefficient was tested according to the pavement permeability coefficient test method in JTG 3450-2019 "Specifications for Field Testing of Highway Subgrade and Pavement"; a pavement permeability meter was used to conduct a constant head permeability test on the coating surface, the permeability volume per unit time was recorded, and the permeability coefficient was calculated in mL / min.

[0096] The anti-skid pendulum value was tested according to the test method for determining the coefficient of friction of road surface using a pendulum apparatus in JTG 3450-2019 "Specifications for Field Testing of Highway Subgrade and Pavement". The anti-skid pendulum value was obtained by measuring the pendulum friction coefficient under wet surface conditions and correcting for the standard temperature. The unit is BPN.

[0097] Preparation Example 1 Add epoxy-modified polyurethane component A to the stirred tank, start stirring, adjust the speed to 400 r / min, and add silane coupling agent KH-792 dropwise at a rate of 0.5 parts / min. After the addition is complete, continue stirring for 5 min. Next, add dioctyl phthalate to the stirred tank, maintaining stirring at 400 r / min for 5 min until the system is homogeneous. Then, add nano-silica and fumed silica in three portions, with a 3-min interval between each addition. After each addition, increase the speed to 800 r / min and stir for 5 min. After all the additions are complete, continue stirring at 800 r / min for 15 min until the powder is completely dispersed without agglomeration or precipitation. Then, reduce the speed to 500 r / min and slowly add epoxy-modified polyurethane component B, stirring for 8 min to ensure complete cross-linking of epoxy-modified polyurethane components A and B. Finally, slowly add polycaprolactone microcapsules, stirring at a low speed of 500 r / min for 5 min to avoid microcapsule breakage. After stirring, test the slurry parameters: solid content 75-80%, viscosity (25℃) 1200-1500 mPa·s, no sediment, no bubbles. After passing the test, filter (80 mesh filter) to obtain the base coat composition. Seal and use within 2 hours to avoid curing failure.

[0098] Preparation Example 2 Modified acrylic emulsion was added to the reactor, and stirring was started at 600 rpm. Aqueous defoamer and hydroxyethyl cellulose were added sequentially, and stirring was continued for 6 minutes until the system was homogeneous and free of bubbles. The stirring speed was maintained at 600 rpm, and carbon aerogel particles were added in two batches, 2 minutes apart, with stirring for 5 minutes after each addition. After all particles were added, the stirring speed was increased to 800 rpm, and stirring was continued for 12 minutes to ensure uniform dispersion of the carbon aerogel. Then, the stirring speed was reduced to 500 rpm, and composite energy storage phase change microcapsules were slowly added, stirring for 8 minutes to prevent microcapsule breakage due to collision. Finally, the stirring speed was reduced to 400 rpm, and a slow-release organic de-icing agent was added, stirring for 5 minutes until the de-icing agent was completely dissolved and the system was homogeneous. After stirring, test the slurry parameters: solid content 65~70%, viscosity (25℃) 800~1000 mPa·s, pH value 7.5~8.5, no stratification, no leakage; after passing the test, filter (60 mesh filter) to obtain the intermediate layer coating composition, seal, and use within 3 hours.

[0099] Preparation Example 3 Add fluorinated siloxane oligomer to a mixing container, turn on a high-speed disperser at 500 r / min, add silicone leveling agent and deionized water, and stir for 8 min until the system is homogeneous. Then, increase the speed to 1000 r / min and add hydrophobically modified nano-zinc oxide and polytetrafluoroethylene micropowder in three batches, 4 min apart, stirring for 6 min after each addition. After all additions are complete, maintain a speed of 1000 r / min and continue stirring for 18 min to ensure complete dispersion of the nanopowder and micropowder without agglomeration. Reduce the speed to 600 r / min and slowly add basalt short fibers, stirring for 6 min to prevent fiber breakage and agglomeration, ensuring uniform fiber dispersion in the system. After stirring, test the slurry parameters: solid content 55-60%, viscosity (25℃) 400-600 mPa·s, no fiber agglomeration, no sedimentation; after passing the test, filter (40 mesh filter) to obtain the topcoat composition, seal, and use within 2 hours.

[0100] Example 1 The road surface is thoroughly washed using a high-pressure water gun (8~10 MPa) to remove dust, oil stains, loose aggregate, fallen leaves, and other debris. Corners and cracks are manually cleaned with a brush to ensure no residual impurities remain. Potholes (depth ≥ 5 mm) are filled with epoxy mortar and compacted to level the surface; cracks (width ≥ 2 mm) are filled with polyurethane sealant, cured, and then ground smooth. The road surface flatness is ensured to be ≤ 3 mm / m. After cleaning, the road surface is allowed to air dry naturally or dried with hot air (temperature ≤ 60℃), with the moisture content strictly controlled to ≤ 5%.

[0101] Subsequently, an angle grinder (diamond grinding disc) was used to lightly grind the entire road surface to a depth of 0.2~0.3 mm to increase the surface roughness (texture depth 0.6~0.8 mm); after grinding, an industrial vacuum cleaner was used to thoroughly remove dust to ensure that the road surface is clean and free of floating dust.

[0102] When spraying the base coat composition, a high-pressure airless sprayer is used. The parameters are: spraying pressure 18~22 MPa, nozzle diameter 0.8 mm, and output 0.8~1.0 L / min. Test spraying is performed to ensure that the spraying is uniform, without missed areas, and without drips.

[0103] Add the base coat composition to the spray gun hopper and spray at a uniform speed, perpendicular to the road's traffic direction, with an overlap width of 5-8 cm and a single coat thickness of 0.8-1.0 mm. During spraying, maintain a distance of 30-40 cm between the spray gun and the road surface, moving it at a uniform speed (0.5-0.8 m / s) to ensure a uniform coating without missed areas, bubbles, or runs. After spraying, allow it to cure naturally at room temperature for 1.5 hours, until it is no longer sticky to the touch and leaves no tacky residue.

[0104] When spraying the intermediate layer coating composition, use a high-pressure airless sprayer and adjust the parameters as follows: spraying pressure 15~18 MPa, nozzle diameter 1.0 mm, and output rate 1.2~1.5 L / min; after passing the test spray, it can be used for standby.

[0105] After the base coat composition has cured to a satisfactory level, immediately spray the intermediate coat composition, perpendicular to the base coat, with an overlap width of 6-10 cm and a single coat thickness of 1.2-1.5 mm. Maintain a distance of 35-45 cm between the spray gun and the road surface, and move the gun at a speed of 0.6-0.9 m / s to ensure uniform coverage of the slurry, without any missed areas or air bubbles. After spraying, allow it to cure naturally for 2 hours (surface dry and not sticky). Then, use an infrared heating plate (1.5 kW, 40-45℃) at a distance of 20-30 cm from the coating, heating at a low temperature for 10 minutes to activate the composite energy storage phase change microcapsules and allow them to fully store energy. After heating, allow it to cool naturally to room temperature and cure until fully cured (≥6 hours).

[0106] When spraying the topcoat composition, adjust the parameters of the high-pressure airless sprayer: spraying pressure 12~15 MPa, nozzle diameter 0.6 mm, and output rate 0.5~0.8 L / min; conduct a test spray to ensure a fine and uniform spray. After the intermediate coat composition has cured successfully, spray the topcoat slurry in two stages: First, spray a thickness of 0.4~0.6 mm, with the spraying direction perpendicular to the intermediate coat, an overlap width of 4~6 cm, a spray gun distance of 25~35 cm, and a moving speed of 0.4~0.6 m / s; after a 30-minute interval, once the first spray is surface dry, perform a second spray with a thickness of 0.4~0.6 mm, for a total thickness of 0.8~1.2 mm, ensuring a uniform surface with no missed areas and no bubbles.

[0107] After the surface coating composition is sprayed, it should be naturally cured at room temperature for 24 hours. During this period, it is strictly forbidden for vehicles to run over it, for pedestrians to step on it, or for rainwater to wash it off. After the curing is completed, the coating will be fully cured and a complete composite energy storage type anti-icing self-healing coating will be formed before traffic can resume.

[0108] The raw materials for each layer of the obtained composite energy storage type anti-icing self-healing coating for road surfaces are as follows: The bonding self-healing undercoat composition comprises 48 parts epoxy-modified polyurethane component A, 24 parts epoxy-modified polyurethane component B; 7.2 parts nano-silica; 9.5 parts polycaprolactone microcapsules; 2.1 parts silane coupling agent; 3.8 parts fumed silica; and 2.4 parts dioctyl phthalate.

[0109] The intermediate layer coating composition of the energy storage and anti-condensation intermediate layer includes 38 parts of modified acrylic emulsion; 25 parts of composite energy storage phase change microcapsules; 11.5 parts of slow-release organic de-icing agent; 5.8 parts of carbon aerogel; 0.9 parts of water-based defoamer; and 1.4 parts of hydroxyethyl cellulose.

[0110] The surface coating composition of the hydrophobic and wear-resistant surface layer includes 34 parts of fluorinated modified siloxane oligomer; 8.3 parts of hydrophobic modified nano zinc oxide; 4.7 parts of basalt short fibers; 6.2 parts of polytetrafluoroethylene micro powder; 0.7 parts of organosilicon leveling agent; and 17.5 parts of deionized water.

[0111] Example 2 The preparation method in this embodiment is the same as in Example 1, except that the raw materials for each layer of the composite energy storage type anti-icing self-healing coating are as follows: The bonding self-healing undercoat composition comprises 52 parts epoxy-modified polyurethane component A, 26 parts epoxy-modified polyurethane component B; 8.5 parts nano-silica; 11 parts polycaprolactone microcapsules; 2.3 parts silane coupling agent; 4.2 parts fumed silica; and 2.7 parts dioctyl phthalate.

[0112] The intermediate coating composition of the energy storage and anti-condensation intermediate layer includes 41 parts modified acrylic emulsion; 27 parts composite energy storage phase change micro-particles; 13 parts slow-release organic de-icing agent; 6.5 parts carbon aerogel; 1.1 parts water-based defoamer; and 1.8 parts hydroxyethyl cellulose.

[0113] The surface coating composition of the hydrophobic and wear-resistant surface layer includes 37 parts of fluorinated modified siloxane oligomer; 9.1 parts of hydrophobic modified nano zinc oxide; 5.3 parts of basalt short fibers; 7.4 parts of polytetrafluoroethylene micro powder; 0.9 parts of organosilicon leveling agent; and 19.2 parts of deionized water.

[0114] Example 3 The preparation method in this embodiment is the same as in Example 1, except that the raw materials for each layer of the composite energy storage type anti-icing self-healing coating are as follows: The bonding self-healing undercoat composition comprises 46 parts epoxy-modified polyurethane component A, 22 parts epoxy-modified polyurethane component B; 6.8 parts nano-silica; 8.8 parts polycaprolactone microcapsules; 1.7 parts silane coupling agent; 3.3 parts fumed silica; and 2.1 parts dioctyl phthalate.

[0115] The intermediate layer coating composition of the energy storage and anti-condensation intermediate layer includes 36 parts modified acrylic emulsion; 23 parts composite energy storage phase change micro-electrode; 10.2 parts slow-release organic de-icing agent; 5.2 parts carbon aerogel; 0.8 parts water-based defoamer; and 1.1 parts hydroxyethyl cellulose.

[0116] The surface coating composition of the hydrophobic and wear-resistant surface layer includes 32 parts of fluorinated modified siloxane oligomer; 7.5 parts of hydrophobic modified nano zinc oxide; 4.2 parts of basalt short fibers; 5.5 parts of polytetrafluoroethylene micro powder; 0.6 parts of organosilicon leveling agent; and 16.3 parts of deionized water.

[0117] Example 4 The preparation method in this embodiment is the same as in Example 1, except that the raw materials for each layer of the composite energy storage type anti-icing self-healing coating are as follows: The bonding self-healing undercoat composition comprises 50 parts epoxy-modified polyurethane component A, 25 parts epoxy-modified polyurethane component B; 7.8 parts nano-silica; 10.2 parts polycaprolactone microcapsules; 2.0 parts silane coupling agent; 4.0 parts fumed silica; and 2.5 parts dioctyl phthalate.

[0118] The intermediate layer coating composition of the energy storage and anti-condensation intermediate layer includes 39 parts of modified acrylic emulsion; 26 parts of composite energy storage phase change micro-electrode; 12.3 parts of slow-release organic de-icing agent; 6.1 parts of carbon aerogel; 1.0 part of water-based defoamer; and 1.6 parts of hydroxyethyl cellulose.

[0119] The surface coating composition of the hydrophobic and wear-resistant surface layer includes 35 parts of fluorinated modified siloxane oligomer; 8.7 parts of hydrophobic modified nano zinc oxide; 5.0 parts of basalt short fibers; 6.8 parts of polytetrafluoroethylene micro powder; 0.8 parts of organosilicon leveling agent; and 18.1 parts of deionized water.

[0120] Example 5 The preparation method in this embodiment is the same as in Example 1, except that the raw materials for each layer of the composite energy storage type anti-icing self-healing coating are as follows: The bonding self-healing undercoat composition comprises 54 parts epoxy-modified polyurethane component A, 27 parts epoxy-modified polyurethane component B; 8.7 parts nano-silica; 11.5 parts polycaprolactone microcapsules; 2.4 parts silane coupling agent; 4.5 parts fumed silica; and 2.8 parts dioctyl phthalate.

[0121] The intermediate layer coating composition of the energy storage and anti-condensation intermediate layer includes 40 parts modified acrylic emulsion; 27.5 parts composite energy storage phase change micro-particles; 13.5 parts slow-release organic de-icing agent; 6.8 parts carbon aerogel; 1.2 parts water-based defoamer; and 1.9 parts hydroxyethyl cellulose.

[0122] The surface coating composition of the hydrophobic and wear-resistant surface layer includes 36 parts of fluorinated modified siloxane oligomer; 9.5 parts of hydrophobic modified nano zinc oxide; 5.7 parts of basalt short fibers; 7.8 parts of polytetrafluoroethylene micro powder; 0.95 parts of organosilicon leveling agent; and 19.5 parts of deionized water.

[0123] Example 6 The preparation method in this embodiment is the same as in Example 1, except that the raw materials for each layer of the composite energy storage type anti-icing self-healing coating are as follows: The bonding self-healing undercoat composition comprises 47 parts epoxy-modified polyurethane component A, 23 parts epoxy-modified polyurethane component B; 7.0 parts nano-silica; 9.2 parts polycaprolactone microcapsules; 1.8 parts silane coupling agent; 3.6 parts fumed silica; and 2.2 parts dioctyl phthalate.

[0124] The intermediate layer coating composition of the energy storage and anti-condensation intermediate layer includes 37 parts modified acrylic emulsion; 24 parts composite energy storage phase change micro-particles; 10.8 parts slow-release organic de-icing agent; 5.5 parts carbon aerogel; 0.85 parts water-based defoamer; and 1.3 parts hydroxyethyl cellulose.

[0125] The surface coating composition of the hydrophobic and wear-resistant surface layer includes 33 parts of fluorinated modified siloxane oligomer; 7.9 parts of hydrophobic modified nano zinc oxide; 4.5 parts of basalt short fibers; 5.9 parts of polytetrafluoroethylene micro powder; 0.65 parts of organosilicon leveling agent; and 17.0 parts of deionized water.

[0126] Example 7 The preparation method in this embodiment is the same as in Example 1, except that the raw materials for each layer of the composite energy storage type anti-icing self-healing coating are as follows: The bonding self-healing undercoat composition comprises 51 parts epoxy-modified polyurethane component A, 25.5 parts epoxy-modified polyurethane component B, 8.1 parts nano-silica, 10.5 parts polycaprolactone microcapsules, 2.2 parts silane coupling agent, 4.1 parts fumed silica, and 2.6 parts dioctyl phthalate.

[0127] The intermediate layer coating composition of the energy storage and anti-condensation intermediate layer includes 39.5 parts modified acrylic emulsion; 25.5 parts composite energy storage phase change micro-particles; 11.8 parts slow-release organic de-icing agent; 6.0 parts carbon aerogel; 0.95 parts water-based defoamer; and 1.5 parts hydroxyethyl cellulose.

[0128] The surface coating composition of the hydrophobic and wear-resistant surface layer includes 34.5 parts of fluorinated modified siloxane oligomer; 8.5 parts of hydrophobic modified nano zinc oxide; 4.9 parts of basalt short fibers; 6.5 parts of polytetrafluoroethylene micro powder; 0.75 parts of organosilicon leveling agent; and 18.3 parts of deionized water.

[0129] Example 8 The preparation method in this embodiment is the same as in Example 1, except that the raw materials for each layer of the composite energy storage type anti-icing self-healing coating are as follows: The bonding self-healing undercoat composition comprises 49 parts epoxy-modified polyurethane component A, 24.5 parts epoxy-modified polyurethane component B, 7.5 parts nano-silica, 9.8 parts polycaprolactone microcapsules, 1.9 parts silane coupling agent, 3.9 parts fumed silica, and 2.3 parts dioctyl phthalate.

[0130] The intermediate layer coating composition of the energy storage and anti-condensation intermediate layer includes 38.5 parts modified acrylic emulsion; 24.8 parts composite energy storage phase change micro-particles; 11.2 parts slow-release organic de-icing agent; 5.7 parts carbon aerogel; 0.9 parts water-based defoamer; and 1.45 parts hydroxyethyl cellulose.

[0131] The topcoat composition of the hydrophobic and wear-resistant surface layer includes 33.8 parts of fluorinated siloxane oligomer; 8.2 parts of hydrophobic modified nano zinc oxide; 4.6 parts of basalt short fibers; 6.1 parts of polytetrafluoroethylene micro powder; 0.7 parts of organosilicon leveling agent; and 17.8 parts of deionized water.

[0132] The self-healing adhesive underlayer, energy-storing anti-coagulation intermediate layer, and hydrophobic wear-resistant surface layer obtained in Examples 1 to 8 were tested respectively, and the results are shown in Tables 1, 2 and 3.

[0133] Table 1. Properties of Hydrophobic and Abrasion-Resistant Surface Layer

[0134] Table 2 Performance of Energy Storage Anti-condensation Intermediate Layer

[0135] Table 3 Performance of self-healing adhesive substrate

[0136] Furthermore, the overall performance of the composite energy storage type anti-icing self-healing coating for road surface obtained in Examples 1 to 8 was tested, and the test results are shown in Table 4.

[0137] Table 4 Overall Coating Performance

[0138] As can be seen from Tables 1 to 4 above, the composite energy storage type anti-icing self-healing coating for pavement prepared by the eight embodiments of this disclosure has excellent compatibility of raw material ratios for each layer, and all key performances meet the standards and show stable performance: the surface layer has a water contact angle of more than 152° and a roll angle of ≤6°, with excellent wear resistance and aging resistance; the intermediate layer has a phase change temperature of -1.5~0.8℃, latent heat ≥185 J / g, slow release period ≥180 days, and freezing point ≤-12.5℃, with outstanding energy storage and anti-icing effects; the bottom layer has a bonding strength ≥3.2 MPa and a self-healing efficiency ≥85%, with reliable bonding and self-healing capabilities; the overall coating has a weather resistance of ≥5 years, excellent waterproof and impermeable properties, and excellent anti-skid performance, which can meet the long-term anti-icing, wear resistance, and self-healing requirements of asphalt and cement concrete pavements in cold regions, and has strong practicality and engineering adaptability.

[0139] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A composite energy storage type pavement anti-icing self-repairing coating, characterized in that, The composite energy storage type anti-icing self-healing coating for road surfaces includes, from top to bottom, a hydrophobic and wear-resistant surface layer, an energy storage and anti-icing intermediate layer, and an adhesive self-healing base layer. The hydrophobic and wear-resistant surface layer comprises fluorinated siloxane oligomers with a surface energy of less than or equal to 22 mN / m. The energy storage and anti-condensation intermediate layer comprises composite energy storage phase change microcapsules with a phase change temperature of -2 to 2°C, and The self-healing adhesive base layer includes polycaprolactone microcapsules, which can rupture and release a self-healing core material that can automatically bond and repair the microcracks when microcracks occur in the road surface.

2. The composite energy-storing pavement anti-icing self-healing coating according to claim 1, characterized in that, The total thickness of the composite energy storage type anti-icing self-healing coating for road surfaces is 2.8~3.7 mm, wherein the thickness of the hydrophobic and wear-resistant top layer is 0.8~1.2 mm, the thickness of the energy storage and anti-icing intermediate layer is 1.2~1.5 mm, and the thickness of the adhesive self-healing underlayer is 0.8~1.0 mm. The interfacial bonding strength between the hydrophobic wear-resistant surface layer, the energy storage anti-icing intermediate layer, and the adhesive self-healing bottom layer is greater than or equal to 3.2 MPa, the interlayer penetration crosslinking depth is 0.1~0.2 mm, and the overall porosity of the composite energy storage type pavement anti-icing self-healing coating is less than or equal to 8%.

3. The composite energy-storing pavement anti-icing self-healing coating according to claim 1, wherein, By weight, the topcoat composition forming the hydrophobic and abrasion-resistant surface layer comprises: 30-38 parts of fluorinated modified siloxane oligomers, 7-10 parts of hydrophobically modified nano zinc oxide, 4-6 parts of basalt short fibers, 5-8 parts of polytetrafluoroethylene micro powder, 0.5 to 1 part silicone leveling agent, and 15-20 parts deionized water The fluorinated siloxane oligomer has a solid content of 55-60%, a fluorine content of 12-15%, and a viscosity of 400-500 mPa·s. The hydrophobically modified nano-zinc oxide has a particle size of 30-50 nm, and is nano-zinc oxide that has been hydrophobically modified with γ-aminopropyltriethoxysilane; and The polytetrafluoroethylene micro powder has a particle size of 2~5 μm and a friction coefficient of less than or equal to 0.

12.

4. The composite energy-storing pavement anti-icing self-healing coating of claim 1, wherein, By weight, the intermediate layer coating composition forming the energy storage and anti-condensation intermediate layer comprises: 35-42 parts modified acrylic emulsion, 22-28 composite energy storage phase change microcapsules, 10-14 parts of slow-release organic de-icing agent, 5-7 parts carbon aerogel particles, 0.8~1.2 parts of water-based defoamer, and 1-2 parts hydroxyethyl cellulose, The modified acrylic emulsion has a solid content of 48-52%, a glass transition temperature of -5-0℃, and a viscosity of 600-800 mPa·s. The composite energy storage phase change microcapsules have a particle size of 80~120 μm, the capsule wall of the composite energy storage phase change microcapsules is melamine-formaldehyde resin, the core material of the composite energy storage phase change microcapsules is a n-octadecane-stearic acid composite phase change material with a mass ratio of (75~85):(15~25), the latent heat of phase change of the composite energy storage phase change microcapsules is 180~210 J / g, and the composite energy storage phase change microcapsules are thermally stable below 120℃; The slow-release organic de-icing agent is a compound mixture of ethylene glycol monomethyl ether and sodium citrate in a mass ratio of (40~50):(50~60), and the slow-release organic de-icing agent has a slow-release period of greater than or equal to 180 days and a freezing point depression of 12~15℃; and The carbon aerogel particles have a particle size of 50-80 μm, a porosity of 85-90%, a specific surface area of ​​600-700 m² / g, and a thermal conductivity of 0.025-0.03 W / (m·K).

5. The composite energy-storing pavement anti-icing self-healing coating of claim 1, wherein, By weight, the undercoat composition forming the self-healing adhesive underlayer comprises: 45-55 parts of epoxy-modified polyurethane component A, 20-28 parts of epoxy-modified polyurethane component B, 6-9 parts nano-silica, 8-12 parts of polycaprolactone microcapsules, 1.5~2.5 parts silane coupling agent, 3-5 parts of fumed silica, and 2-3 parts dioctyl phthalate, Wherein, the epoxy-modified polyurethane component A is an epoxy-modified polyurethane prepolymer with an epoxy value of 0.22~0.26 eq / 100g, and the viscosity of the epoxy-modified polyurethane component A is 2,500~3,000 mPa·s. The epoxy-modified polyurethane component B is an aliphatic amine curing agent with an amine value of 380~420 mgKOH / g, and the viscosity of the epoxy-modified polyurethane component B is 800~1,000 mPa·s. The polycaprolactone microcapsules have a particle size of 100-150 μm, the capsule wall of the polycaprolactone microcapsules contains sodium alginate, the core material of the polycaprolactone microcapsules is a polyurethane prepolymer with a solid content of 45-50%, and the strength of the polycaprolactone microcapsules is greater than or equal to 0.8 MPa. The fumed silica has a particle size of 10-20 nm and a specific surface area of ​​300-350 m². 2 / g.

6. A method for preparing a composite energy storage type anti-icing self-healing coating for road surfaces according to any one of claims 1 to 5, characterized in that, The method includes: S1. Prepare the primer coating composition; S2. Prepare the intermediate layer coating composition; S3. Preparation of a topcoat composition; and S4. The base coat composition, the intermediate coat composition and the top coat composition are sequentially sprayed onto the road surface and allowed to cure naturally for 24 hours to obtain the composite energy storage type anti-icing self-healing coating.

7. The method of claim 6, wherein, Step S1 includes: S11. Under stirring conditions, add silane coupling agent and dioctyl phthalate to epoxy-modified polyurethane component A to obtain a mixture containing epoxy-modified polyurethane component A. S12. Under stirring conditions, nano-silica is added to the mixture containing epoxy-modified polyurethane component A in three portions, with an interval of 3 minutes between each addition, to obtain a mixture containing nano-silica. S13. Under stirring at 500 r / min, epoxy-modified polyurethane component B is slowly added to the mixture containing nano-silica for 8 minutes to obtain a crosslinked mixture; and S14. Polycaprolactone microcapsules are slowly added to the crosslinked mixture under stirring at 500 r / min for 5 minutes to obtain the underlying coating composition.

8. The method of claim 6, wherein, Step S2 includes: S21. Add an aqueous defoamer and hydroxyethyl cellulose to the modified acrylic emulsion to obtain a bubble-free mixed emulsion. S22. Carbon aerogel particles are added to the bubble-free mixed emulsion in two separate additions, with a 2-minute interval between each addition, to obtain a mixed emulsion containing carbon aerogel particles. S23. Composite energy storage phase change microcapsules are added to the mixed emulsion containing carbon aerogel particles under stirring at 500 r / min to obtain a mixed emulsion containing the composite energy storage phase change microcapsules; and S24. Add a slow-release organic de-icing agent to the mixed emulsion containing the composite energy storage phase change microcapsules while stirring at 400 r / min to obtain the intermediate layer coating composition.

9. The method of claim 6, wherein, Step S3 includes: S31. Add organosilicon leveling agent and deionized water to fluorinated siloxane oligomers to obtain fluorinated siloxane oligomer solution. S32. A mixture of hydrophobically modified nano-zinc oxide and polytetrafluoroethylene micropowder is added to the fluorinated siloxane oligomer solution in three separate additions, with a 4-minute interval between each addition, to obtain a solution containing the powder; and S33. Basalt short fibers are added to the powder-containing solution under stirring at 600 r / min to obtain the surface coating composition.

10. A cement / asphalt concrete pavement, characterized by, The cement / asphalt concrete pavement is covered with a composite energy storage type anti-icing self-healing coating, wherein the composite energy storage type anti-icing self-healing coating is a composite energy storage type anti-icing self-healing coating according to any one of claims 1 to 5 or a composite energy storage type anti-icing self-healing coating prepared by any one of claims 6 to 8.

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