Super-hydrophobic coating spraying liquid, preparation and construction method thereof and super-hydrophobic coating

Abstract

The invention relates to the technical field of super-hydrophobic materials, and particularly discloses a super-hydrophobic coating spraying liquid, a preparation and construction method thereof and a super-hydrophobic coating. The super-hydrophobic coating spraying liquid provided by the invention is prepared from the following components: nano SiO2 which is modified by a silane coupling agent containing amino / alkoxy and a silane coupling agent containing long fluorine chain / long-chain alkane step by step, microcapsules which are sequentially modified by the silane coupling agent containing amino / alkoxy and a dispersing agent for the second time, and a solvent which is added into the microcapsules, and a thermosetting resin. The nano SiO2 and the microcapsules which are subjected to multiple modification have good hydrophobicity, and nano metal particles loaded in the microcapsules form an anti-algae active center of the super-hydrophobic coating. And the super-hydrophobic coating prepared by using the super-hydrophobic coating spraying liquid organically combines hydrophobicity and an anti-algae active center together, so that an efficient and long-acting anti-algae effect can be realized, and the problems of short pollution flashover prevention time and poor algae removal performance of the existing super-hydrophobic coating are solved.

Description

Technical Field

[0001] The present application relates to the technical field of super-hydrophobic material preparation, and in particular to a super-hydrophobic coating spray liquid, a preparation and construction method thereof, and a super-hydrophobic coating. Background Art

[0002] With the rapid advancement of industrialization and urbanization, power transmission lines in regions characterized by high temperature and high humidity, such as southern China, are facing increasingly severe challenges from biofouling. For example, composite insulators are susceptible to the growth of green algae, which not only affects the appearance of transmission lines but also absorbs large amounts of water and nutrients during their growth and metabolism, causing the insulator surface to remain permanently moist. This significantly increases the surface conductivity of the insulator, ultimately inducing insulation flashover, which seriously impacts the normal operation of the power system.

[0003] Traditional anti-pollution flashover strategies mainly include regular cleaning of insulators and coating with anti-pollution flashover paint. However, these conventional methods have many limitations. For example: regular cleaning of insulators requires a lot of manpower and is extremely labor-intensive. It also involves equipment, chemicals, and other expenses, resulting in high costs; the chemicals used in the cleaning process may also pollute the surrounding environment, and the cleaning effect is difficult to maintain for a long time. Green algae will re-attach to the surface of the insulator in a short period of time; although anti-pollution flashover paint can play a protective role to a certain extent, it also faces problems such as high cost and the attenuation of protective effect over time. Based on the limitations of the above-mentioned traditional anti-pollution flashover strategies, superhydrophobic coatings have attracted widespread attention due to their outstanding hydrophobicity and self-cleaning properties, which can effectively inhibit the attachment and growth of green algae.

[0004] Although superhydrophobic coatings have shown potential for application in flashover prevention, their hydrophobic durability and active algae removal capabilities still need to be improved. Green algae secrete extracellular polymers such as organic acids during their growth process, which gradually erode the micro-nanostructure of the superhydrophobic surface, causing its hydrophobic properties to gradually decrease. Furthermore, superhydrophobic coatings themselves lack effective mechanisms for actively removing green algae, making efficient removal difficult once they attach to the surface. Therefore, the development of superhydrophobic coatings with long-lasting algae removal capabilities has become a key issue in this field. Summary of the Invention

[0005] In view of this, the purpose of this application is to provide a super-hydrophobic coating spray liquid, its preparation and construction method, and a super-hydrophobic coating, which are used to solve the problems of short anti-flash pollution time and poor algae removal performance of existing super-hydrophobic coatings.

[0006] To achieve the above technical objectives, the present application provides a method for preparing a super-hydrophobic coating spray liquid, comprising the following steps:

[0007] Step S1-1, preparing hydrophobic nano-SiO2: immersing the nano-SiO2 in an organic solvent in which a silane coupling agent containing an amino group / alkoxy group is dissolved, heating, stirring, and centrifuging the resulting solid matter, washing, and drying the resulting solid matter to obtain a primary modified nano-SiO2; adding the primary modified nano-SiO2 to an organic solvent in which a silane coupling agent containing a long fluorine chain / long chain alkane is dissolved, heating, stirring, and centrifuging the resulting solid matter, washing, and drying the resulting solid matter to obtain a secondary modified nano-SiO2;

[0008] Step S1-2, preparing a super-hydrophobic coating substrate: mixing the secondary modified nano-SiO2 with a thermosetting resin, heating and stirring, to obtain a super-hydrophobic coating substrate;

[0009] Step S2, preparing microcapsules:

[0010] The nano-metal particle suspension, chitosan organic solution and emulsifier are mixed evenly, a cross-linking agent is added, and the mixture is heated, stirred, filtered, washed and dried to obtain microcapsules;

[0011] Step S3-1, placing the microcapsules in an organic solvent in which an amino / alkoxy-containing silane coupling agent is dissolved, and heating and stirring to obtain primary modified microcapsules; Step S3-2, uniformly mixing the primary modified microcapsules with a dispersant to obtain secondary modified microcapsules;

[0012] Step S3-3, uniformly mixing the secondary modified microcapsules with the super-hydrophobic coating substrate to obtain a super-hydrophobic coating spray liquid.

[0013] Furthermore, the nano-metal particle suspension is formed by mixing nano-metal particles with a solvent; the nano-metal particles include one of nano-carbon copper powder, nano-titanium dioxide, nano-silver, and nano-copper oxide.

[0014] Furthermore, the amino / alkoxy-containing silane coupling agent is selected from one of KH-550, KH-560, KH-570, and KH-590; the long fluorine chain / long chain alkane-containing silane coupling agent is selected from one of perfluorodecyltriethoxysilane, octadecyltrimethoxysilane, and trifluoropropyltrimethoxysilane; the thermosetting resin is selected from at least one of epoxy resin and silicone resin; the emulsifier is selected from at least one of Span-80 and Tween-80; the cross-linking agent is selected from one of glyoxal, glutaraldehyde, and adipaldehyde; and the dispersant is selected from one of phosphate ester and alkylphenol polyoxyethylene ether phosphate.

[0015] Furthermore, the amino / alkoxy-containing silane coupling agent is KH-550; the long fluorine chain / long chain alkane-containing silane coupling agent is perfluorodecyltriethoxysilane; and the thermosetting resin is epoxy resin.

[0016] Furthermore, the mass ratio of the secondary modified microcapsules to the superhydrophobic coating substrate is (1~3):7.

[0017] Furthermore, nano-SiO2 is prepared by the following steps: ammonia water and an organic solvent are evenly mixed to form an alkaline hydrolysis environment, and ethyl orthosilicate is placed in the alkaline hydrolysis environment for hydrolysis reaction to obtain nano-SiO2.

[0018] The present application provides a super-hydrophobic coating spray liquid prepared by the above-mentioned preparation method.

[0019] The present application provides a method for applying a super-hydrophobic coating spray liquid, comprising the following steps:

[0020] Step S1, silicone rubber surface pretreatment and spray suspension preparation:

[0021] Silicone rubber surface pretreatment: polishing the silicone rubber surface with sandpaper of decreasing grit, then ultrasonically cleaning the polished silicone rubber surface with anhydrous ethanol, and drying it after cleaning to obtain the silicone rubber for use;

[0022] Preparation of spray suspension: mixing the super-hydrophobic coating spray liquid with the curing agent, heating and stirring to obtain a spray suspension;

[0023] Step S2, preparation of super-hydrophobic coating:

[0024] The spray suspension is sprayed on the spare silicone rubber in multiple times, and dried after spraying to obtain a super hydrophobic coating with controlled-release algae removal function.

[0025] Furthermore, the mass ratio of the super-hydrophobic coating spray liquid to the curing agent is 10:1.

[0026] The present application provides a coating comprising the following components: a curing agent and a super-hydrophobic coating spray liquid; the coating is coated on the outer surface of a silicone rubber insulator for algae removal and flashover prevention, and the thickness of the coating is 0.1 mm.

[0027] In summary, the present application provides a super hydrophobic coating spray liquid, which is composed of the following components: nano-SiO2 modified by amino / alkoxy-containing silane coupling agents and long fluorine chain / long chain alkane-containing silane coupling agents, microcapsules modified by amino / alkoxy-containing silane coupling agents and dispersants, and thermosetting resin. Not only significantly enhanced the nano The hydrophobicity of the coating is enhanced, and its interfacial compatibility and binding strength with thermosetting resins are significantly improved through chemical bonding mechanisms. The secondary modified microcapsules, thanks to their multiple surface modifications, are able to stably disperse in thermosetting resin systems and form a tight bond with the resin matrix. Furthermore, the nano-metal particles loaded within the microcapsules serve as the coating's anti-algae active centers, inhibiting algae growth through various pathways, including direct sterilization, photocatalytic oxidation, and ion interference.

[0028] In the preparation process of super-hydrophobic coating, the spraying process used in this study has significant advantages. The process is simple to operate, has relatively low requirements for spraying equipment and working environment, and can significantly reduce production and construction costs. The super-hydrophobic coating prepared by this process effectively reduces the surface energy of the coating due to its high hydrophobicity, inhibits the initial attachment of green algae, and thus achieves a passive anti-fouling function; at the same time, the chitosan microcapsule wall in the coating can be corroded by the organic acids produced by algae metabolism, prompting the degradation of the microcapsules to release nano-metal particles, thereby achieving active removal of algae. This process constructs a "passive anti-fouling-active sterilization" synergistic mechanism. Through the dual effects of physical barrier and chemical killing, it maintains the stability of the coating's algae removal effect for a long time, significantly improving the durability of the algae removal effect.

[0029] Compared with the existing technology, this study prepared nanoparticles through multiple modification strategies. The microcapsules possess excellent dispersibility, hydrophobicity, and excellent bonding with thermosetting resins. Furthermore, the use of nano-metal particles in place of traditional chemical algaecides not only achieves the coating's long-lasting algae control function but also avoids the potential environmental harm of traditional chemical agents. This represents a dual breakthrough in both algae control efficiency and environmental friendliness, providing an innovative solution for the field of super-hydrophobic algae control coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0031] Figure 1 A schematic diagram of the preparation process of a super-hydrophobic coating with controlled-release algae removal function provided in an embodiment of the present application;

[0032] Figure 2 A schematic diagram of a preparation process of a microcapsule provided in an embodiment of the present application;

[0033] Figure 3A schematic diagram of a preparation process of a super-hydrophobic coating spray liquid provided in an embodiment of the present application;

[0034] Figure 4 A schematic diagram of the preparation process of a super-hydrophobic coating provided in an embodiment of the present application. DETAILED DESCRIPTION

[0035] The following will clearly and completely describe the technical solutions of the embodiments of this application in conjunction with the accompanying drawings. Obviously, the embodiments described are part of the embodiments of this application, not all of them. Based on the embodiments in this specification, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection requested by this application.

[0036] The sources of all raw materials in the present invention are not particularly limited and can be purchased on the market or prepared according to conventional methods known to those skilled in the art.

[0037] See also Figure 1 The present application provides a method for preparing a super-hydrophobic coating spray liquid, comprising the following steps:

[0038] Step S1, preparing a super-hydrophobic coating substrate:

[0039] Step S1-1, preparing hydrophobic nano-SiO2: immersing the nano-SiO2 in an organic solvent in which a silane coupling agent containing an amino group or an alkoxy group is dissolved, heating, stirring, and centrifuging, and then washing and drying the solid matter to obtain a primary modified nano-SiO2; adding the primary modified nano-SiO2 to an organic solvent in which a silane coupling agent containing a long fluorine chain or a long chain alkane is dissolved, heating, stirring, and centrifuging, and then washing and drying the solid matter to obtain a secondary modified nano-SiO2;

[0040] Step S1-2, preparing a super-hydrophobic coating substrate: mixing the secondary modified nano-SiO2 with a thermosetting resin, heating and stirring, to obtain a super-hydrophobic coating substrate;

[0041] Step S2, preparing microcapsules, the preparation process is as follows Figure 2 :

[0042] The nano-metal particle suspension, chitosan organic solution and emulsifier are mixed evenly, and then a cross-linking agent is added, followed by heating, stirring, filtering, washing and drying to obtain microcapsules;

[0043] Step S3, prepare super hydrophobic coating spray liquid, the preparation process is as follows Figure 3 :

[0044] Step S3-1, placing the microcapsules in an organic solvent in which an amino / alkoxy-containing silane coupling agent is dissolved, heating and stirring to obtain primary modified microcapsules;

[0045] Step S3-2, uniformly mixing the primary modified microcapsules with a dispersant to obtain secondary modified microcapsules;

[0046] Step S3-3, uniformly mixing the secondary modified microcapsules with the super-hydrophobic coating substrate to obtain a super-hydrophobic coating spray liquid.

[0047] It should be noted that the amino and alkoxy groups in the amino / alkoxy-containing silane coupling agent are easily hydrolyzed to form silanol groups ( ), the silanol groups can react with the hydroxyl groups on the surface of the nanoparticles to form stable silicon-oxygen bonds ( ), which changes the surface properties of the nanoparticles from hydrophilic to organophilic, thereby reducing the agglomeration of nanoparticles caused by factors such as surface charge and improving the dispersibility of nanoparticles in organic media. Silane coupling agents containing long fluorine chains / long chain alkanes have low surface energy due to their long fluorine chains and long chain alkane groups. At the same time, long fluorine chains and long chain alkanes usually have relatively regular chemical structures and large steric hindrances, which increase the contact angle of water on the surface and help improve hydrophobicity. Nano-SiO2 modified by the step-by-step use of the above two silane coupling agents not only exhibits excellent hydrophobic properties, but also achieves high binding properties with the thermosetting resin matrix. Similarly, the microcapsule system that is secondary modified with an amino / alkoxy silane coupling agent and a dispersant also exhibits excellent hydrophobic properties and excellent binding effects with thermosetting resins.

[0048] In some embodiments, the nano-metal particle suspension is formed by mixing nano-metal particles with a solvent; the nano-metal particles include one of nano-carbon copper powder, nano-titanium dioxide, nano-silver, and nano-copper oxide.

[0049] It should be noted that the nano-metal particles used all have broad-spectrum algae removal properties, but their mechanism of action and additional functions vary depending on the material properties. Nano-carbon copper powder can react with organic acids (such as formic acid, acetic acid, etc.) produced by algae metabolism to release copper ions ( ), these ions disrupt chloroplast function by interfering with the electron transport chain of the photosynthetic system, while simultaneously acting on cell membrane ion channels to achieve algaecide. Furthermore, nano-carbon copper powder can effectively regulate the surface potential of the coating, reducing electrostatic adsorption effects and significantly improving antifouling performance. In addition to its direct contact bactericidal properties, nano-titanium dioxide's photocatalytic properties can generate reactive oxygen species (ROS) under light conditions, killing algae through oxidative pathways. Nano-silver, with its excellent antimicrobial activity, can achieve broad-spectrum algaecide even with trace additions. Nano-copper oxide, on the other hand, primarily works through the release of copper ions, and its algaecide mechanism is similar to that of nano-carbon copper powder.

[0050] In some embodiments, the amino / alkoxy-containing silane coupling agent is selected from one of KH-550, KH-560, KH-570, and KH-590; the long fluorine chain / long chain alkane-containing silane coupling agent is selected from one of perfluorodecyltriethoxysilane, octadecyltrimethoxysilane, and trifluoropropyltrimethoxysilane; the thermosetting resin is selected from at least one of epoxy resin and silicone resin; the emulsifier is selected from at least one of Span-80 and Tween-80; the cross-linking agent is selected from one of glyoxal, glutaraldehyde, and adipaldehyde; and the dispersant is selected from one of phosphate ester and alkylphenol polyoxyethylene ether phosphate.

[0051] Preferably, the amino / alkoxy-containing silane coupling agent is KH-550; the long fluorine chain / long chain alkane-containing silane coupling agent is perfluorodecyltriethoxysilane; and the thermosetting resin is epoxy resin.

[0052] It should be noted that the main purpose of using KH-550 to modify nano-SiO2 is to improve the dispersibility of nano-SiO2 in polar solvents, and the purpose of using perfluorodecyltriethoxysilane for secondary modification is to improve the hydrophobicity of the once-modified nano-SiO2. This method of sequentially using dispersion and hydrophobic modification can make nano-SiO2 both dispersible and super-hydrophobic.

[0053] In a specific embodiment of the present application, in step S2, the amino / alkoxy-containing silane coupling agent is KH-560. Compared with KH-560, KH-570, and KH-590, KH-550 containing an amino group can form hydrogen bonds with the hydroxyl groups on the microcapsule wall formed by chitosan, and can also provide stronger chemical adsorption force for the binding of the silane coupling agent to the microcapsule wall through electrostatic interaction.

[0054] In a specific embodiment of the present application, the dispersant is a phosphate ester, because the phosphate ester has excellent chemical stability in a non-polar system, is not prone to degradation reactions, and does not adversely affect the hydrophobic properties of the coating.

[0055] In a specific embodiment of the present application, the thermosetting resin is bisphenol A epoxy resin, which has good compatibility with the secondary modified nano-SiO2.

[0056] In some embodiments, the mass ratio of the secondary modified microcapsules to the superhydrophobic coating substrate is (1-3):7.

[0057] In some embodiments, nano-SiO2 is prepared by the following steps: ammonia water and an organic solvent are uniformly mixed to form an alkaline hydrolysis environment, and ethyl orthosilicate is placed in the alkaline hydrolysis environment for hydrolysis reaction to obtain nano-SiO2.

[0058] It should be noted that the nano-SiO2 involved in the present invention is independently prepared and is not a commercially available product. Due to different preparation processes, the particle size, surface chemical properties and dispersibility of commercially available nano-SiO2 all vary to varying degrees, making it difficult to accurately control the quality of nano-SiO2 in actual application. The homemade nano-SiO2 of the present application can strictly control the purity and surface functional groups of nano-SiO2 by selecting the preparation method and reaction conditions. In particular, in the present embodiment, the nano-SiO2 generated under the conditions of an alkaline hydrolysis environment has silanol groups ( ), Siloxane ( ) and other active groups. These active groups help improve the dispersibility of SiO2 in polar organic solvents (such as anhydrous ethanol), providing abundant sites for subsequent modification; on the other hand, they also help improve the bonding ability with thermosetting resins.

[0059] The embodiments of the present application provide a super-hydrophobic coating spray liquid prepared by the above-mentioned preparation method.

[0060] See also Figure 4 The present invention provides a method for applying a super-hydrophobic coating spray liquid, comprising the following steps:

[0061] Step S1, silicone rubber surface pretreatment and spray suspension preparation:

[0062] Silicone rubber surface pretreatment: polishing the silicone rubber surface with sandpaper of decreasing grit, then ultrasonically cleaning the polished silicone rubber surface with anhydrous ethanol, and drying it after cleaning to obtain the silicone rubber for use;

[0063] Preparation of spray suspension: mixing the super-hydrophobic coating spray liquid with the curing agent, heating and stirring to obtain a spray suspension;

[0064] Step S2, preparation of super-hydrophobic coating:

[0065] The spray suspension is sprayed on the spare silicone rubber in multiple times, and dried after spraying to obtain a super hydrophobic coating with controlled-release algae removal function.

[0066] In a specific embodiment of the present application, sandpaper with a grit size of 600, 1000, or 1500 can be used to quickly and carefully polish the silicone rubber surface to improve the adhesion of the coating.

[0067] In a specific embodiment of the present application, the spray suspension is divided into several equal parts and sprayed in batches, and each spraying operation needs to be carried out after the coating formed by the previous spraying is dry.

[0068] In a specific embodiment of the present application, the mass ratio of the super-hydrophobic coating spray liquid to the curing agent is 10:1, and the curing agent is W593 modified amine.

[0069] An embodiment of the present application provides a coating comprising the following components: a super-hydrophobic coating spray liquid and a curing agent; the coating is coated on the outer surface of a silicone rubber insulator for algae removal and flashover prevention, and the thickness of the coating is 0.1 mm.

[0070] It should be noted that the algae removal principle of the super-hydrophobic coating prepared in this application is as follows: First, the super-hydrophobic coating effectively inhibits the initial attachment of green algae by reducing its surface energy through its high hydrophobicity; second, for a small number of green algae that break through the hydrophobic barrier and attach, their metabolic activities secrete organic acids (including formic acid, acetic acid, etc.), which gradually degrade the capsule wall structure of the chitosan microcapsule, resulting in the partial exposure of the coated nano-metal particles, which are in direct contact with the green algae or the organic matter secreted by the green algae. The exposed nano-metal particles achieve algae removal through the following pathways: (1) direct contact sterilization; (2) photocatalytic oxidation reaction (such as Produces reactive oxygen species under light); (3) metal cations (such as 、 ) interferes with key physiological processes in algae cells. This process embodies the synergistic mechanism of "passive antifouling and active sterilization," achieving long-lasting algae removal.

[0071] The applicant further provides the following reference specific embodiments to describe the present invention. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0072] Example 1

[0073] This embodiment provides a method for preparing a super-hydrophobic coating with a controlled-release algae removal function, and the specific steps are as follows:

[0074] Step S1, preparing a super-hydrophobic coating substrate;

[0075] Step S1-1, preparation of nano-SiO2:

[0076] Add 10 mL of ammonia water to 1000 mL of anhydrous ethanol and stir with a magnetic stirrer for 15 minutes to form a uniform alkaline hydrolysis environment; add 100 g of ethyl orthosilicate to the alkaline hydrolysis environment and then stir at 25°C for 5 hours to obtain nano-SiO2;

[0077] Step S1-2, preparation of hydrophobic nano-SiO2:

[0078] Step S1-2-1, immersing the nano-SiO2 in anhydrous ethanol, first using ultrasonic oscillation for 10 minutes, and then using a magnetic stirrer to stir for 1 hour to uniformly disperse the nano-SiO2 in the anhydrous ethanol, thereby obtaining a nano-SiO2 suspension;

[0079] Step S1-2-2, heating the nano-SiO2 suspension to 65°C, then adding 20g of silane coupling agent KH-550, and stirring with a magnetic stirrer at a constant temperature of 65°C for 4h. After stirring, centrifugation is performed for 15 min. After centrifugation, the solid matter is washed twice with anhydrous ethanol by centrifugation, and then dried at 60°C for 2h to obtain a modified nano-SiO2.

[0080] Step S1-2-3, adding the primary modified nano-SiO2 to a mixed solution containing 10 g of perfluorodecyltriethoxysilane and 100 mL of anhydrous ethanol, heating the mixed solution to 50°C and stirring it with a magnetic stirrer at a constant temperature of 50°C for 4 hours. After stirring, centrifugation is performed for 15 minutes. After centrifugation, the solid matter is washed twice by centrifugation with anhydrous ethanol, and then dried at 60°C for 2 hours to obtain secondary modified nano-SiO2;

[0081] Step S1-3, preparing a super-hydrophobic coating substrate:

[0082] The secondary modified nano-SiO2 was mixed with 500 g of bisphenol A epoxy resin, and then stirred at a constant temperature of 75° C. for 5.0 h to obtain a super-hydrophobic coating substrate.

[0083] Step S2, microcapsule preparation:

[0084] Step S2-1, preparing nano-carbon copper powder dispersion and chitosan solution:

[0085] 50 g of nano-carbon copper powder was mixed with 100 mL of deionized water and ultrasonically vibrated for 30 min to obtain a nano-carbon copper powder dispersion with a mass concentration of 500 g / L.

[0086] Dissolve 5 g of chitosan in 200 mL of dilute acetic acid and stir to form a chitosan solution with a mass concentration of 25 g / mL;

[0087] Step S2-2, 100 mL of the nano-carbon copper powder dispersion was mixed with 200 mL of the chitosan solution, and then 2 g of Span-80 and 2 g of Tween-80 were added, and the mixture was stirred with a magnetic device at a constant temperature of 25° C. for 1.0 h to form an emulsion;

[0088] Step S2-3, adding 1 g of glutaraldehyde to the emulsion, and adjusting the pH of the emulsion to 3.5, then stirring at a constant temperature of 80° C. for 5.0 h, and then filtering, washing, and drying to obtain microcapsules.

[0089] Step S3, preparing a super-hydrophobic coating spray liquid:

[0090] Step S3-1, adding the microcapsules to 1 L of a 1% by mass KH550 solution, adjusting the pH of the solution to 3.5, and stirring at 60° C. for 2.0 h using a magnetic stirrer to obtain primary modified microcapsules;

[0091] Step S3-2: uniformly mix the primary modified microcapsules and the dispersant in a mass ratio of 5:1 to obtain secondary modified microcapsules.

[0092] Step S3-3, adding the secondary modified microcapsules to the super-hydrophobic coating substrate, using a high shear mixer at a speed of 5000~10000 r / min for 30 minutes to obtain a super-hydrophobic coating spray liquid; wherein the mass ratio of the secondary modified microcapsules to the super-hydrophobic coating substrate is 1:7.

[0093] This embodiment uses the super-hydrophobic coating spray liquid prepared above to prepare a super-hydrophobic coating, comprising the following steps:

[0094] Step S4-1, silicone rubber surface pretreatment and spray suspension preparation:

[0095] Silicone rubber surface pretreatment: The silicone rubber surface was polished using 600, 1000, and 1500 mesh sandpaper in sequence, and then ultrasonically cleaned with anhydrous ethanol for 5 minutes. After cleaning, the silicone rubber was dried to obtain the spare silicone rubber;

[0096] Preparation of spray suspension: The superhydrophobic coating spray liquid and W593 modified amine were mixed in a mass ratio of 10:1 and stirred at 40°C for 1.5 h to obtain a spray suspension;

[0097] Step S4-2, preparation of super-hydrophobic coating: the spray suspension is divided into two equal parts, and a spray gun with a caliber of 0.7 mm is used to evenly spray one portion of the spray liquid on the spare silicone rubber at a spraying pressure of 0.2 MPa. During spraying, the distance between the muzzle and the surface of the silicone rubber is controlled at 25-30 cm, and the spray gun moves at a uniform speed of 4-6 cm / s; after the first spraying is completed, wait for 30 minutes, and after the spray liquid is dried, another portion of the spray liquid is evenly sprayed on the silicone rubber. After the second spraying is completed, the silicone rubber is placed in a drying oven at a temperature of 50 ° C and dried for 2.0 hours to obtain a super-hydrophobic coating with controlled-release algae removal function.

[0098] Performance test: Take the silicone rubber with a super-hydrophobic coating prepared in this example, cover the surface of the super-hydrophobic coating with green algae, and then place the silicone rubber with the green algae on the surface of the super-hydrophobic coating in a light incubator at a temperature of 24°C for 48 hours. After the incubation, slowly rinse the surface of the super-hydrophobic coating with deionized water. After the rinsing is completed, the surface contact angle of the super-hydrophobic coating is tested, and the green algae coverage is simultaneously measured. After testing, the surface contact angle of the super-hydrophobic coating of this example after 48 hours of artificial green algae contamination is 148.6°, and the green algae coverage is 10%.

[0099] Example 2

[0100] The difference from Example 1 is that the added mass is different during the preparation of microcapsules, as follows:

[0101] Step S2, microcapsule preparation:

[0102] Step S2-1, preparing nano-carbon copper powder dispersion and chitosan solution:

[0103] 100 g of nano-carbon copper powder was mixed with 200 mL of deionized water and ultrasonically vibrated for 30 min to obtain a nano-carbon copper powder dispersion with a mass concentration of 500 g / L.

[0104] Dissolve 10 g of chitosan in 400 mL of dilute acetic acid to form a chitosan solution with a mass concentration of 25 g / mL;

[0105] Step S2-2, 100 mL of the nano-carbon copper powder dispersion was mixed with 200 mL of the chitosan solution, 4 g of Span-80 and 4 g of Tween-80 were added, and the mixture was stirred with a magnetic stirrer at a constant temperature of 25° C. for 1.0 h to form an emulsion;

[0106] Step S2-3, adding 2 g of glutaraldehyde to the emulsion, and adjusting the pH of the emulsion to 3.5, then stirring at a constant temperature of 80° C. for 5.0 h, and then filtering, washing, and drying to obtain microcapsules.

[0107] That is, in step S3, the mass ratio of the secondary modified microcapsules to the super-hydrophobic coating substrate is 2:7.

[0108] Performance test: After the super-hydrophobic coating with controlled-release algae removal function prepared in this example was contaminated with artificial green algae for 48 hours, its surface water contact angle was 155.3° and the green algae coverage was 6%.

[0109] Example 3

[0110] The difference from Example 1 is that the added mass is different during the preparation of microcapsules, as follows:

[0111] Step S2, microcapsule preparation:

[0112] Step S2-1, preparing nano-carbon copper powder dispersion and chitosan solution:

[0113] 150 g of nano-carbon copper powder was mixed with 300 mL of deionized water and ultrasonically vibrated for 30 min to obtain a nano-carbon copper powder dispersion with a mass concentration of 500 g / L.

[0114] Dissolve 15 g of chitosan in 600 mL of dilute acetic acid to form a chitosan solution with a mass concentration of 25 g / mL;

[0115] Step S2-2, 100 mL of the nano-carbon copper powder dispersion was mixed with 200 mL of the chitosan solution, 6 g of Span-80 and 6 g of Tween-80 were added, and the mixture was stirred with a magnetic stirrer at a constant temperature of 25° C. for 1.0 h to form an emulsion;

[0116] Step S2-3, adding 3 g of glutaraldehyde to the emulsion, and adjusting the pH of the emulsion to 3.5, then stirring at a constant temperature of 80° C. for 5.0 h, and then filtering, washing, and drying to obtain microcapsules.

[0117] That is, in step S3, the mass ratio of the secondary modified microcapsules to the super-hydrophobic coating substrate is 3:7.

[0118] Performance test: After the super hydrophobic coating with controlled release algae removal function prepared in this example was contaminated by artificial green algae for 48 hours, its surface water contact angle was , the rolling angle is , the green algae coverage is 3%.

[0119] Comparative Example 1

[0120] The difference from Example 3 is that no microcapsules were added to the super-hydrophobic coating. After being contaminated with artificial green algae for 48 hours, the surface water contact angle of the super-hydrophobic coating with controlled-release algae removal prepared in this example was 87.4°, and the green algae coverage was 80%.

[0121] Comparative Example 2

[0122] The difference from Example 3 is that the nano-SiO2 is not modified. After the super-hydrophobic coating with controlled-release algae removal function prepared in this example was contaminated by artificial green algae for 48 hours, its surface water contact angle was , the rolling angle is , the green algae coverage is 80%.

[0123] Comparative Example 3

[0124] The difference from Example 3 is that the nano-SiO2 is only modified once with KH-550. The super hydrophobic coating with controlled release algae removal function prepared in this example was contaminated with artificial green algae for 48 hours. Its surface water contact angle is , the rolling angle is , the green algae coverage is 50%.

[0125] Comparative Example 4

[0126] The difference from Example 3 is that the nano-SiO2 is modified only once with perfluorodecyltriethoxysilane. The super-hydrophobic coating with controlled-release algae removal function prepared in this example has a surface water contact angle of 0.040 after being contaminated by artificial green algae for 48 hours. , the rolling angle is , the green algae coverage is 30%.

[0127] The variables and experimental results of the above embodiments and comparative examples are integrated to obtain Table 1.

[0128] Table 1

[0129]

[0130] As can be seen from Table 1, the super-hydrophobic coatings prepared in Examples 1 to 3 have a surface water contact angle of more than 145° after being contaminated by artificial green algae for 48 hours. The super-hydrophobic coating prepared in Comparative Example 1 does not contain secondary modified microcapsules, and the surface water contact angle of the super-hydrophobic coating after being contaminated by artificial green algae for 48 hours is 87.4°, indicating that the hydrophobic effect of the super-hydrophobic coating prepared by relying solely on modified nano-SiO2 to provide hydrophobicity is not good; the nano-SiO2 in the super-hydrophobic coating prepared in Comparative Example 2 is not modified, and its surface water contact angle after being contaminated by artificial green algae is 87.4°. The water contact angle of the super-hydrophobic coating surface after 48 hours is 98.5°, indicating that the hydrophobic effect of the prepared super-hydrophobic coating is not ideal only by relying on the hydrophobicity provided by the secondary modified microcapsules. The hydrophobicity of the super-hydrophobic coating can only be greatly improved when the modified nano-SiO2 and modified microcapsules exist at the same time. This effect may be due to the good synergistic effect between the nano-SiO2 after multiple modifications, the active groups on the surface of the modified microcapsules, and the thermosetting resin, which jointly improve the hydrophobicity and algae removal effect of the super-hydrophobic coating.

[0131] The above are only preferred embodiments of the present application and are not intended to limit the present invention. Although the present application has been described in detail with reference to examples, those skilled in the art can still modify the technical solutions described in the aforementioned examples or make equivalent replacements for some of the technical features therein. However, any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a super-hydrophobic coating spray liquid, characterized in that, The following steps are involved: Step S1-1, preparing hydrophobic nano-SiO2: immersing the nano-SiO2 in an organic solvent in which a silane coupling agent containing an amino group / alkoxy group is dissolved, heating, stirring, and centrifuging the resulting solid matter, washing, and drying the resulting solid matter to obtain a primary modified nano-SiO2; adding the primary modified nano-SiO2 to an organic solvent in which a silane coupling agent containing a long fluorine chain / long chain alkane is dissolved, heating, stirring, and centrifuging the resulting solid matter, washing, and drying the resulting solid matter to obtain a secondary modified nano-SiO2; Step S1-2, preparing a super-hydrophobic coating substrate: mixing the secondary modified nano-SiO2 with a thermosetting resin, heating and stirring, to obtain a super-hydrophobic coating substrate; Step S2, preparing microcapsules: uniformly mixing the nano-metal particle suspension, chitosan organic solution, and emulsifier, adding a cross-linking agent, heating and stirring, filtering, washing, and drying to obtain microcapsules; Step S3-1, placing the microcapsules in an organic solvent in which an amino / alkoxy-containing silane coupling agent is dissolved, and heating and stirring to obtain primary modified microcapsules; Step S3-2, uniformly mixing the primary modified microcapsules with a dispersant to obtain secondary modified microcapsules; Step S3-3, uniformly mixing the secondary modified microcapsules with the super-hydrophobic coating substrate to obtain a super-hydrophobic coating spray liquid.

2. The method for preparing a super-hydrophobic coating spray liquid according to claim 1, wherein: The nano-metal particle suspension is formed by mixing nano-metal particles and a solvent; The nano metal particles include one of nano carbon copper powder, nano titanium dioxide, nano silver and nano copper oxide.

3. The method for preparing a super-hydrophobic coating spray liquid according to claim 1, wherein: The amino / alkoxy-containing silane coupling agent is selected from one of KH-550, KH-560, KH-570, and KH-590; The silane coupling agent containing a long fluorine chain / long chain alkane is selected from one of perfluorodecyltriethoxysilane, octadecyltrimethoxysilane and trifluoropropyltrimethoxysilane; The thermosetting resin is selected from at least one of epoxy resin and silicone resin; The emulsifier is selected from at least one of Span-80 and Tween-80; The cross-linking agent is selected from one of glyoxal, glutaraldehyde and adipaldehyde; The dispersant is selected from one of phosphate ester and alkylphenol polyoxyethylene ether phosphate.

4. The method for preparing a super-hydrophobic coating spray liquid according to claim 3, wherein: The amino / alkoxy-containing silane coupling agent is KH-550; the long fluorine chain / long chain alkane-containing silane coupling agent is perfluorodecyltriethoxysilane; and the thermosetting resin is epoxy resin.

5. The method for preparing a super-hydrophobic coating spray liquid according to claim 1, wherein: The mass ratio of the secondary modified microcapsules to the super-hydrophobic coating substrate is (1-3):

7.

6. The method for preparing a super-hydrophobic coating spray liquid according to claim 1, wherein: The nano-SiO2 is prepared by the following steps: ammonia water and an organic solvent are uniformly mixed to form an alkaline hydrolysis environment, and ethyl orthosilicate is placed in the alkaline hydrolysis environment for hydrolysis reaction to obtain nano-SiO2.

7. A super-hydrophobic coating spray liquid obtained by the preparation method according to any one of claims 1 to 6.

8. A construction method for a super-hydrophobic coating spray liquid as claimed in claim 7, characterized in that, The following steps are involved: Step S1, silicone rubber surface pretreatment and spray suspension preparation: Silicone rubber surface pretreatment: polishing the silicone rubber surface with sandpaper of decreasing grit, then ultrasonically cleaning the polished silicone rubber surface with anhydrous ethanol, and drying it after cleaning to obtain the silicone rubber for use; Preparation of spray suspension: mixing the super-hydrophobic coating spray liquid with the curing agent, heating and stirring to obtain a spray suspension; Step S2, preparation of super-hydrophobic coating: The spray suspension is sprayed on the spare silicone rubber in multiple times, and dried after spraying to obtain a super hydrophobic coating with controlled-release algae removal function.

9. The construction method of the super-hydrophobic coating spraying liquid according to claim 8, wherein The mass ratio of the super-hydrophobic coating spray liquid to the curing agent is 10:

1.

10. A coating, characterized in that The invention comprises the following components: a curing agent and a super-hydrophobic coating spray liquid obtained by the preparation method according to any one of claims 1 to 6; The coating is coated on the outer surface of the silicone rubber insulator for removing algae and preventing flashover pollution, and the thickness of the coating is 0.1 mm.

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