CN113667349A - Super-hydrophilic coating and preparation method thereof - Google Patents
Super-hydrophilic coating and preparation method thereof Download PDFInfo
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Abstract
The present disclosure presents a method for preparing a superhydrophilic coating and the corresponding superhydrophilic coating. The method comprises the following steps: stirring and dispersing the nano particles in an alcohol solution, adding a surface treatment agent, and stirring and reacting to assemble the nano particles into a strip shape; adjusting the pH value of the solution, adding a surface treatment agent, and stirring for reaction to assemble the strip-shaped nano particles into hollow nano particle micelles; separating, drying and grinding the stirred solution to prepare hollow nano particle micelles with controllable sizes and shapes; adding the aqueous flatting agent, the aqueous dispersing agent, the aqueous thickening agent, the aqueous defoaming agent, the aqueous film forming agent and the deionized water into a reaction kettle for stirring; and adding the prepared hollow nano particle micelles into a reaction kettle, and stirring for reaction to prepare the super-hydrophilic coating. The novel micro-nano structure synthesis process is adopted, and the nano particles are assembled into hollow micelles with controllable sizes and shapes, so that the cured coating has super-hydrophilic characteristics.
Description
Technical Field
The disclosure relates to the technical field of new chemical materials and coatings, in particular to a method for preparing a super-hydrophilic coating and the super-hydrophilic coating prepared by the method.
Background
As one of the most interesting and promising research and application objects in the field of bionics, a superhydrophilic surface refers to a solid surface having a micro-nano structure that can cause water drops on the surface to spread out by itself, and generally has a contact angle of less than 10 ° with respect to the water drops. Due to the unique nano characteristic function of the super-hydrophilic surface, the super-hydrophilic surface can be applied to the high technical fields of buildings, transportation, biomedical materials, information technology, energy technology and the like and national defense construction.
Disclosure of Invention
The present disclosure presents a method for preparing a superhydrophilic coating and the superhydrophilic coating prepared by the method.
According to an aspect of the present disclosure, the method for preparing a superhydrophilic coating includes: stirring and dispersing the nano particles in an alcohol solution, adding a surface treatment agent for carrying out a first stirring reaction to assemble the nano particles into a strip shape; regulating the pH value of the solution, adding a surface treatment agent, and carrying out secondary stirring reaction to assemble the strip-shaped nano particles into hollow nano particle micelles with controllable sizes and shapes; separating, drying and grinding the stirred solution to prepare hollow nano particle micelles with controllable sizes and shapes; adding the aqueous flatting agent, the aqueous dispersing agent, the aqueous thickening agent, the aqueous defoaming agent, the aqueous film forming agent and the deionized water into a reaction kettle for stirring; and adding the prepared hollow nano particle micelles into a reaction kettle, and stirring for reaction to prepare the super-hydrophilic coating.
Optionally, the method further includes: and adding the prepared hollow nano particle micelle into a reaction kettle for stirring reaction, adding the nano bonding agent into the reaction kettle for stirring reaction, and improving the adhesive force of the prepared super-hydrophilic coating by using the nano bonding agent.
Optionally, in the above method, the step of stirring and dispersing the nanoparticles in the alcohol solution, and adding the surface treatment agent to perform a first stirring reaction to assemble the nanoparticles into a strip specifically includes: setting the stirring reaction time to be 12-24 h; after the stirring reaction is finished, the pH value of the solution is adjusted to be 8-9, so that the solution is alkaline, the assembly of the nano particles is stopped, and the long-strip-shaped nano particles are kept uniform in the solution through stirring.
Optionally, in the above method, adjusting the PH of the solution, and adding the surface treatment agent to perform a second stirring reaction to assemble the elongated nanoparticles into hollow nanoparticle micelles with controllable size and shape specifically includes: adjusting the pH value of the solution to 6-7 to make the solution acidic, adding a surface treatment agent for stirring reaction for 12-48 h, and assembling the strip-shaped nanoparticles into hollow nanoparticle micelles; and adjusting the pH value of the solution to 8-9 to make the solution alkaline and stirring to prevent further assembly of the hollow nanoparticle micelles.
Optionally, in the above method, the stirring reaction time of the nano bonding agent in the reaction kettle is set to be 24-96 h.
Optionally, in the above method, the alcohol solution is selected from one or more of ethanol, isopropanol, methanol, butanol, and propanol, wherein the weight ratio of the surface treatment agent to the nanoparticles is 0.1-10% and 5-30%, respectively, and the balance is alcohol.
Optionally, in the above method, the surface treatment agent comprises the following components in parts by weight: 1-8% of polyethylene oxide or polyvinyl ether; tartaric acid or salicylic acid 0.5-2.5%; threonine or isoleucine 0.05-0.5%; the balance being toluene.
Optionally, in the above method, the material of the nanoparticle is selected from one or more of titanium dioxide, silicon dioxide and aluminum oxide, and the particle diameter of the nanoparticle is 5nm to 50 nm; the shape of the assembled hollow nano particle micelle is one or more of a hollow square, a hollow rhombus, a hollow pentagon, a hollow hexagon and a circular ring, the wall thickness of the hollow nano particle micelle is 100 nm-2000 nm, and the size of the hole is 300 nm-20000 nm.
Optionally, in the above method, the weight ratio of each component is as follows: 0.05-0.2% of water-based flatting agent, 0.03-0.3% of water-based dispersant, 0.06-0.6% of water-based thickener, 0.02-0.2% of water-based defoamer, 0.04-0.4% of water-based film-forming agent, 0.05-12% of nano bonding agent, 0.1-20% of hollow nano particle micelle and the balance of deionized water.
Optionally, in the above method, the nano-bonding agent comprises the following components in parts by weight: 5-30% of modified acrylate or modified polyurethane; acetic acid or oxalic acid 0.5-2%; 0.05 to 0.5 percent of silane coupling agent; 1-2.5% of silanol and 0.7-3% of glycol or glycerol; 0.5 to 2.5 percent of curing agent; the balance of ethanol or deionized water.
Optionally, in the above method, the silane coupling agent is selected from one or more of KH550, KH560, KH 570.
According to another aspect of the present disclosure, there is also provided a superhydrophilic coating prepared according to the above method.
Optionally, after the super-hydrophilic coating is cured on the surface of the substrate, a super-hydrophilic coating with a water drop contact angle of less than 10 degrees can be obtained.
For example, the super-hydrophilic coating can be formed on the surfaces of hard substrates such as building exterior walls, glass, metal, ceramic, stone, concrete and plastics, and flexible substrates such as plastic films, paper, non-woven fabrics, various fabrics (such as cotton fabrics, polyester fabrics, acrylic fabrics, polypropylene fabrics, and the like), composite films, sponges and the like by spraying, dipping, brushing or roller coating, and can form the super-hydrophilic coating with the characteristics of high adhesion, high wear resistance and high weather resistance after being cured for 24 hours at room temperature (20-25 ℃). And when the ambient temperature is lower than room temperature, the curing time is correspondingly prolonged.
Compared with the prior art, the method for preparing the super-hydrophilic coating and the prepared super-hydrophilic coating provided by the disclosure have at least the following advantages:
(1) by adopting a new micro-nano structure synthesis process, nano particles are assembled into hollow micelles with controllable sizes and shapes, so that the coating has super-hydrophilic characteristics;
(2) by adopting a strong nano bonding process and introducing chemical bonds into the nano particles and the micelle structures thereof, the bonding force between the nano particles and the micelle structures is greatly improved, so that the super-hydrophilic coating with the characteristics of high adhesion, high wear resistance and high weather resistance can be formed after curing for 24 hours at room temperature (20-25 ℃); and
(3) the coating product is a water-based environment-friendly formula and has no environmental pollution.
Drawings
Fig. 1 is a schematic diagram of the general flow of the method for preparing a super-hydrophilic coating with adjustable transparency proposed by the present disclosure.
Fig. 2 is a measurement result of a contact angle of a water droplet on a surface of a super-hydrophilic coating prepared according to an example of the method proposed by the present disclosure.
Fig. 3 is a measurement result of a contact angle of a water droplet on a surface of a super hydrophilic coating prepared according to another example of the method proposed by the present disclosure.
Detailed Description
The present disclosure presents a method for preparing a superhydrophilic coating. As shown in fig. 1, the method mainly includes: s101, stirring and dispersing the nano particles in an alcohol solution, adding a surface treatment agent to carry out a first stirring reaction, and assembling the nano particles into a strip shape; s110, adjusting the pH value of the solution, adding a surface treating agent, and carrying out a second stirring reaction to assemble the strip-shaped nano particles into hollow nano particle micelles with controllable sizes and shapes; s120, separating, drying and grinding the stirred solution to prepare hollow nano particle micelles with controllable sizes and shapes; s130, adding the aqueous flatting agent, the aqueous dispersing agent, the aqueous thickening agent, the aqueous defoaming agent, the aqueous film forming agent and the deionized water into a reaction kettle for stirring; and S140, adding the prepared hollow nano particle micelles into a reaction kettle, and stirring for reaction to prepare the super-hydrophilic coating.
The following examples are merely illustrative of the technical ideas and features of the present disclosure and should not be construed as limiting the present disclosure. Modifications and substitutions to the disclosed methods, steps, or conditions may be made without departing from the spirit and nature of the disclosure. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Specifically, as an example, the method for preparing the super-hydrophilic coating includes the steps of:
(1) dispersing the nanoparticles in an alcohol solution by stirring (for example, magnetic stirring), adjusting the temperature of the solution to be 40-100 ℃, adding a surface treating agent, stirring for reaction for 12-24 hours, and then adjusting the pH value of the solution to be 8-9, thereby assembling the nanoparticles into a strip shape;
(2) adjusting the pH value of the solution to 6-7, adding a surface treating agent, stirring for 12-48 h, and adjusting the pH value of the solution to 8-9, so that the strip-shaped nano particles are assembled into hollow micelles;
(3) sequentially carrying out separation, drying (removing polymers, organic matters, solvents and the like) and grinding to obtain hollow micelles with controllable sizes and shapes;
(4) adding an aqueous flatting agent (at least one of polyester modified organic siloxane and polyether modified organic silicon), an aqueous dispersing agent (at least one of sodium cellulose sulfate, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate), an aqueous thickening agent (at least one of gelatin, polyvinylpyrrolidone, polyvinyl alcohol or polyacrylamide), an aqueous defoaming agent (at least one of emulsified silicone oil or polydimethylsiloxane), an aqueous film forming agent (at least one of propylene glycol butyl ether, ethylene glycol butyl ether and 2.2.4 trimethyl-1.3-pentanediol monoisobutyrate) and deionized water into a reaction kettle at the reaction temperature of 30-70 ℃ and uniformly stirring, and then dispersing the obtained hollow nanoparticles into the hollow micelles and uniformly stirring;
(5) adding a nano bonding agent, stirring and reacting for 24-96h to obtain the water-based super-hydrophilic coating.
Optionally, in the above step, the alcohol solution is one or more of ethanol, isopropanol, methanol, butanol, propanol, etc., and the silane coupling agent is one or more of KH550, KH560, KH570, etc.; the weight ratio of the surface treating agent to the nano particles is 0.1-10% and 5-30%, and the balance is alcohol.
Alternatively, in the above step, the surface treatment agent includes polyethylene oxide or polyvinyl ether or the like (1 to 8%), tartaric acid or salicylic acid or the like (0.5 to 2.5%), threonine or isoleucine or the like (0.05 to 0.5%), and the balance being toluene.
Optionally, in the above step, the nanoparticles are one or more of titanium dioxide, silicon dioxide, aluminum oxide, etc., and the particle size is 5nm to 50 nm; the nano particles are assembled by the surface treating agent to obtain hollow micro-clusters with holes, the shapes of the hollow micro-clusters can be hollow square, hollow rhombus, hollow pentagon/hexagon, circular ring and the like, the wall thickness of the shapes is 100 nm-2000 nm, and the hole size is 300 nm-20000 nm. The basic mechanism of assembly is as follows: when the nano particles in the mixed solution of polymer macromolecules (such as polyethylene oxide or polyvinyl ether) and a small amount of protein molecules approach each other gradually in the stirring process, the catalysis of specific acid (such as tartaric acid or salicylic acid) generates osmotic pressure-negative pressure near the nano particles, and the negative pressure further extrudes the polymer and protein macromolecules existing among the nano particles, so that the nano particles approach each other, namely the nano particles are assembled. The size and shape of the region of negative pressure are directly related to the size of the nanoparticle, the size and quantity ratio of the polymer macromolecules to the protein molecules, the pH value of the solution, the temperature, the assembly time and other factors, so that the size and shape of the nanoparticle assembly can be adjusted by changing the factors. Specifically, the assembly process of the micelles such as the hollow square, the hollow rhombus, the hollow pentagon/hexagon, the ring shape and the like is as follows: firstly, adding a surface treating agent into an alcohol solution with nano particles, assembling the nano particles into a strip shape under the catalysis of specific acid, then adding alkali such as ammonia water or sodium hydroxide solution into the solution, adjusting the pH value of the solution to 8-9, stopping the assembly of the nano particles and continuously stirring, and keeping the strip-shaped nano particles in the solution uniformly; then, adding acetic acid or oxalic acid to adjust the pH value of the solution to 6-7, adding a surface treating agent to enable the strip-shaped nano particles to approach each other and tend to form the polygonal or circular shape, adding alkali again after the external dimension meets the requirement (for example, dimension detection can be carried out through a scanning electron microscope), adjusting the pH value of the solution to 8-9, and stopping assembly so that polymers and protein macromolecules which are not extruded out still exist in the polygonal or circular central area; and then sequentially carrying out separation, drying (removing polymers, organic matters, solvents and the like) and grinding, thus finally preparing the hollow square, hollow rhombus, hollow pentagon/hexagon, circular micelle and the like.
Optionally, the weight ratio of each component in the step (4) is as follows: 0.05 to 0.2 percent of water-based flatting agent, 0.03 to 0.3 percent of water-based dispersant, 0.06 to 0.6 percent of water-based thickener, 0.02 to 0.2 percent of water-based defoamer, 0.04 to 0.4 percent of water-based film-forming agent, 0.05 to 12 percent of nano bonding agent, 0.1 to 20 percent of nano particles and the balance of deionized water, and the total is 100 percent.
Optionally, in the above step, the nano bonding agent includes modified acrylate or modified polyurethane (5-30%), acetic acid or oxalic acid (0.5-2%), silane coupling agent (0.05-0.5%), silanol (1-2.5%), ethylene glycol or glycerol (0.7-3%) and curing agent (0.5-2.5%), and the rest is ethanol or deionized water. The modified acrylate or modified polyurethane has good weather resistance and adhesion, inorganic nanoparticles and the modified acrylate or modified polyurethane are respectively bonded through inorganic groups and organic groups of the silane coupling agent, and chemical bonds are introduced into the nanoparticle and micelle structures thereof, so that the bonding force between the nanoparticles and the micelle structures is greatly improved, and the cured coating has the characteristics of high adhesion, high wear resistance and high weather resistance.
In specific application, the super-hydrophilic coating prepared by the preparation method provided by the disclosure can be formed into films on the surfaces of hard substrates such as building outer walls, glass, metal, ceramic, stone, concrete and plastic, and flexible substrates such as plastic films, paper, non-woven fabrics, various fabrics (such as cotton fabrics, polyester fabrics, acrylic fabrics, polypropylene fabrics and the like), composite films and sponges in a spraying, dip-coating, brush coating or roller coating mode, and is cured for 24 hours at room temperature (20-25 ℃) to form the super-hydrophilic coating with high adhesion, high wear resistance and high weather resistance. And when the ambient temperature is lower than room temperature, the curing time is correspondingly prolonged.
Optionally, after the coating is cured on the surface of the substrate, the super-hydrophilic coating with the water drop contact angle smaller than 10 degrees can be obtained.
As another example, the present disclosure provides a method of forming a superhydrophilic coating, comprising the steps of:
(1) dispersing the nanoparticles in an alcohol solution by stirring (for example, magnetic stirring), adjusting the temperature of the solution to be 40-100 ℃, adding a surface treating agent, stirring for reaction for 12-24 hours, and then adjusting the pH value of the solution to be 8-9, thereby assembling the nanoparticles into a strip shape;
(2) adjusting the pH value of the solution to 6-7, adding a surface treating agent, stirring for 12-48 h, and adjusting the pH value of the solution to 8-9, so that the strip-shaped nano particles are assembled into hollow micelles;
(3) sequentially carrying out separation, drying (removing polymers, organic matters, solvents and the like) and grinding to obtain hollow micelles with controllable sizes and shapes;
(4) adding an aqueous flatting agent (at least one of polyester modified organic siloxane and polyether modified organic silicon), an aqueous dispersing agent (at least one of sodium cellulose sulfate, sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate), an aqueous thickening agent (at least one of gelatin, polyvinylpyrrolidone, polyvinyl alcohol or polyacrylamide), an aqueous defoaming agent (at least one of emulsified silicone oil or polydimethylsiloxane), an aqueous film forming agent (at least one of propylene glycol butyl ether, ethylene glycol butyl ether and 2.2.4 trimethyl-1.3-pentanediol monoisobutyrate) and deionized water into a reaction kettle at the reaction temperature of 30-70 ℃ and uniformly stirring, and then dispersing the obtained hollow nanoparticles into the hollow micelles and uniformly stirring;
(5) adding a nano bonding agent, stirring and reacting for 24-96h to obtain the water-based super-hydrophilic coating.
(6) The prepared super-hydrophilic coating is subjected to film formation on the upper surface of a base material in a spraying, dipping, brushing or roller coating mode, and is cured for 24 hours at room temperature (20-25 ℃) to form a super-hydrophilic coating with the characteristics of high adhesion, high wear resistance and high weather resistance; and when the ambient temperature is lower than room temperature, the curing time is correspondingly prolonged.
Alternatively, the substrate includes, but is not limited to, a rigid substrate such as an exterior wall of a building, glass, metal, ceramic, stone, concrete, and plastic, and a flexible substrate such as a plastic film, paper, a non-woven fabric, various fabrics (such as cotton fabric, polyester fabric, acrylic fabric, polypropylene fabric, and the like), a composite film, and a sponge.
After the super-hydrophilic coating prepared by the method provided by the disclosure is cured on the surface of the substrate, the super-hydrophilic coating with a water drop contact angle smaller than 10 degrees can be obtained.
Optionally, in the above step, the alcohol solution is one or more of ethanol, isopropanol, methanol, butanol, propanol, etc., and the silane coupling agent is one or more of KH550, KH560, KH570, etc.; the weight ratio of the surface treating agent to the nano particles is 0.1-10% and 5-30%, and the balance is alcohol.
Alternatively, in the above step, the surface treatment agent includes polyethylene oxide or polyvinyl ether or the like (1 to 8%), tartaric acid or salicylic acid or the like (0.5 to 2.5%), threonine or isoleucine or the like (0.05 to 0.5%), and the balance being toluene.
Optionally, in the above step, the nanoparticles are one or more of titanium dioxide, silicon dioxide, aluminum oxide, etc., and the particle size is 5nm to 50 nm; the nano particles are assembled by the surface treating agent to obtain hollow micro-clusters with holes, the shapes of the hollow micro-clusters can be hollow square, hollow rhombus, hollow pentagon/hexagon, circular ring and the like, the wall thickness of the shapes is 100 nm-2000 nm, and the hole size is 300 nm-20000 nm. The basic mechanism of assembly is as follows: when the nano particles in the mixed solution of polymer macromolecules (such as polyethylene oxide or polyvinyl ether) and a small amount of protein molecules approach each other gradually in the stirring process, the catalysis of specific acid (such as tartaric acid or salicylic acid) generates osmotic pressure-negative pressure near the nano particles, and the negative pressure further extrudes the polymer and protein macromolecules existing among the nano particles, so that the nano particles approach each other, namely the nano particles are assembled. The size and shape of the region of negative pressure are directly related to the size of the nanoparticle, the size and quantity ratio of the polymer macromolecules to the protein molecules, the pH value of the solution, the temperature, the assembly time and other factors, so that the size and shape of the nanoparticle assembly can be adjusted by changing the factors. The assembly process of the micelles such as the hollow square, the hollow rhombus, the hollow pentagon/hexagon, the circular ring and the like is as follows: firstly, adding a surface treating agent into an alcohol solution with nano particles, assembling the nano particles into a strip shape under the catalysis of specific acid, then adding alkali such as ammonia water or sodium hydroxide solution into the solution, adjusting the pH value of the solution to 8-9, stopping the assembly of the nano particles and continuously stirring, and keeping the strip-shaped nano particles in the solution uniformly; then, adding acetic acid or oxalic acid to adjust the pH value of the solution to 6-7, adding a surface treating agent to enable the strip-shaped nano particles to approach each other and tend to form the polygonal or circular shape, adding alkali again after the external dimension meets the requirement (for example, dimension detection can be carried out through a scanning electron microscope), adjusting the pH value of the solution to 8-9, and stopping assembly so that polymers and protein macromolecules which are not extruded out still exist in the polygonal or circular central area; and then sequentially carrying out separation, drying (removing polymers, organic matters, solvents and the like) and grinding, thus finally preparing the hollow square, hollow rhombus, hollow pentagon/hexagon, circular micelle and the like.
Optionally, the weight ratio of each component in the step (4) is as follows: 0.05 to 0.2 percent of water-based flatting agent, 0.03 to 0.3 percent of water-based dispersant, 0.06 to 0.6 percent of water-based thickener, 0.02 to 0.2 percent of water-based defoamer, 0.04 to 0.4 percent of water-based film-forming agent, 0.05 to 12 percent of nano bonding agent, 0.1 to 20 percent of nano particles and the balance of deionized water, and the total is 100 percent.
Optionally, in the above step, the nano bonding agent includes modified acrylate or modified polyurethane (5-30%), acetic acid or oxalic acid (0.5-2%), silane coupling agent (0.05-0.5%), silanol (1-2.5%), ethylene glycol or glycerol (0.7-3%) and curing agent (0.5-2.5%), and the rest is ethanol or deionized water. The modified acrylate or modified polyurethane has good weather resistance and adhesion, inorganic nanoparticles and the modified acrylate or modified polyurethane are respectively bonded through inorganic groups and organic groups of the silane coupling agent, and chemical bonds are introduced into the nanoparticle and micelle structures thereof, so that the bonding force between the nanoparticles and the micelle structures is greatly improved, and the cured coating has the characteristics of high adhesion, high wear resistance and high weather resistance.
In order to facilitate an understanding of the method for preparing a superhydrophilic coating presented in this disclosure, a detailed description is provided below by way of example. It should be understood that the embodiments of the disclosure are merely illustrative for the purpose of illustrating the principles of the technology and are not intended to limit the scope of the invention in any way.
Example 1
Firstly, dispersing titanium dioxide nanoparticles (5-10nm and 2g) in an alcohol solution of isopropanol and propanol (80ml:40ml) by stirring (for example, magnetic stirring), adjusting the temperature of the solution to 50 ℃, adding 0.5g of a surface treating agent (polyethylene oxide 1%, oleic acid 0.5%, tartaric acid 0.5%, threonine 0.1% and the balance toluene), stirring at the speed of 800r/min for 12 hours, adding ammonia water, adjusting the pH value of the solution to 8-9, and assembling the nanoparticles into a long strip (the diameter is 20-30nm and the length is 100-150 nm); then, adding acetic acid, adjusting the pH value of the solution to 6-7, adding 0.8g of surface treating agent, stirring at the speed of 600r/min for 24 hours, adding ammonia water, adjusting the pH value of the solution to 8-9, and assembling the strip-shaped nano particles into annular micelles. Finally, sequentially carrying out separation, drying (removing polymers, organic matters, solvents and the like) and grinding to prepare the ring-shaped micelle (the wall thickness of the ring is 200-300nm, and the diameter of the inner hole of the ring is 350-700 nm);
secondly, adding a water-based flatting agent (0.05 g of flatting agent is polyether), a water-based dispersing agent (0.03g of cellulose sodium sulfosulfonate), a water-based thickening agent (0.04g), a water-based defoaming agent (0.03g), a water-based film forming agent (0.06g) and deionized water (110g) into a reaction kettle at the reaction temperature of 60 ℃, uniformly stirring, and then dispersing the obtained titanium dioxide ring-shaped micelles therein, and uniformly stirring; and finally, adding 0.06g of nano bonding agent (5% of modified acrylate, 0.5% of acetic acid, 0.1% of silane coupling agent, 1% of silanol, 0.7% of glycol, 0.5% of curing agent and the balance of ethanol), stirring at the speed of 600r/min, and stirring for reacting for 24 hours to obtain the water-based and milky super-hydrophilic coating.
When in specific application, the obtained water-based and milky super-hydrophilic coating can be sprayed on the surface of a glass substrate and cured for 24 hours at the room temperature of 20 ℃ to obtain the super-hydrophilic coating with the characteristics of high adhesion, high wear resistance and high weather resistance.
In this example, the contact angle of the coating layer with respect to a water droplet was 5.5 ° as measured by a contact angle measuring instrument, as shown in fig. 2.
Example 2
Firstly, dispersing silicon dioxide nano particles (5-10nm and 2g) in an alcohol solution of isopropanol and propanol (60ml:60ml) by stirring (for example, magnetic stirring), adjusting the temperature of the solution to 60 ℃, adding 0.4g of a surface treating agent (polyethylene oxide 1.5%, oleic acid 0.7%, tartaric acid 0.8%, threonine 0.3% and the balance toluene), stirring at the speed of 1000r/min, adding ammonia water after the reaction time is 24 hours, adjusting the pH value of the solution to 8-9, and assembling the nano particles into a long strip shape (the diameter is 30-40nm and the length is 150-200 nm); adding oxalic acid, adjusting the pH value of the solution to 6-7, adding 0.6g of the surface treating agent, stirring at the speed of 800r/min for 24 hours, adding ammonia water, adjusting the pH value of the solution to 8-9, and assembling the strip-shaped nano particles into hollow pentagonal micelles. Finally, sequentially carrying out separation, drying (removing polymers, organic matters, solvents and the like) and grinding to prepare hollow pentagonal micelles (the wall thickness of the pentagonal micelle is 300-1200 nm, and the diameter of the inner hole is 700-1200 nm);
secondly, adding an aqueous flatting agent (0.06g of flatting agent is polyether), an aqueous dispersing agent (0.05 g of cellulose sodium sulfosulfonate), an aqueous thickening agent (0.07g), an aqueous defoaming agent (0.04g), an aqueous film forming agent (0.09g) and deionized water (110g) into a reaction kettle at the reaction temperature of 60 ℃, uniformly stirring, and then dispersing the obtained hollow pentagonal silicon dioxide micelle into the mixture, and uniformly stirring; and finally, adding 0.08g of nano bonding agent (7% of modified acrylate, 0.4% of acetic acid, 0.3% of silane coupling agent, 3% of silanol, 0.9% of glycol, 1% of curing agent and the balance of ethanol), stirring at the speed of 700r/min, and stirring for 24 hours to obtain the water-based and milky super-hydrophilic coating.
When in specific application, the obtained water-based and milky super-hydrophilic coating is sprayed on the surface of a glass substrate and cured for 24 hours at the room temperature of 20 ℃ to obtain the super-hydrophilic coating with the characteristics of high adhesion, high wear resistance and high weather resistance.
In this example, the contact angle of the coating layer with respect to a water droplet was 8.1 ° as measured by a contact angle measuring instrument, as shown in fig. 3.
According to the method for preparing the super-hydrophilic coating and the prepared super-hydrophilic coating, the novel micro-nano structure synthesis process is adopted, and the nano particles are assembled into the hollow micelles with controllable sizes and shapes, so that the coating has super-hydrophilic characteristics; and by adopting a strong nano bonding process and introducing chemical bonds into the nano particles and the micelle structures thereof, the bonding force between the nano particles and the micelle structures is greatly improved, so that the super-hydrophilic coating with the characteristics of high adhesion, high wear resistance and high weather resistance can be formed after curing for 24 hours at room temperature (20-25 ℃). In addition, the coating product prepared by the preparation method provided by the disclosure is a water-based environment-friendly formula and has no environmental pollution.
The foregoing represents only alternative embodiments of the present disclosure and structural changes, modifications, finishes and the like may be made by anyone without departing from the principles of the present disclosure and these changes, modifications, finishes and the like are deemed to be within the scope of protection of the present disclosure.
A number of implementations have been described. Nevertheless, it will be understood that various modifications may be made. For example, elements of different implementations may be combined, supplemented, modified or removed to produce other implementations. Further, those of skill in the art will understand that other structures and processes may be substituted for those disclosed and the resulting implementations will perform at least substantially the same function and achieve at least substantially the same result as the disclosed implementations in at least substantially the same way. Accordingly, these and other implementations are contemplated by this application.
Claims (12)
1. A method for preparing a superhydrophilic coating, comprising:
stirring and dispersing the nano particles in an alcohol solution, adding a surface treatment agent for carrying out a first stirring reaction to assemble the nano particles into a strip shape;
regulating the pH value of the solution, adding a surface treatment agent, and carrying out secondary stirring reaction to assemble the strip-shaped nano particles into hollow nano particle micelles with controllable sizes and shapes;
separating, drying and grinding the stirred solution to prepare hollow nano particle micelles with controllable sizes and shapes;
adding the aqueous flatting agent, the aqueous dispersing agent, the aqueous thickening agent, the aqueous defoaming agent, the aqueous film forming agent and the deionized water into a reaction kettle for stirring; and
and adding the prepared hollow nano particle micelles into a reaction kettle, and stirring for reaction to prepare the super-hydrophilic coating.
2. The method of claim 1, further comprising:
and adding the prepared hollow nano particle micelle into a reaction kettle for stirring reaction, adding the nano bonding agent into the reaction kettle for stirring reaction, and improving the adhesive force of the prepared super-hydrophilic coating by using the nano bonding agent.
3. The method of claim 1, wherein the step of dispersing the nanoparticles in the alcohol solution with stirring, adding the surface treatment agent to perform a first stirring reaction to assemble the nanoparticles into a strip shape comprises:
setting the stirring reaction time to be 12-24 h;
after the stirring reaction is finished, the pH value of the solution is adjusted to be 8-9, so that the solution is alkaline, the assembly of the nano particles is stopped, and the long-strip-shaped nano particles are kept uniform in the solution through stirring.
4. The method of claim 1, wherein the adjusting the PH of the solution and adding the surface treatment agent to perform a second stirring reaction to assemble the elongated nanoparticles into hollow nanoparticle micelles with controllable size and shape comprises:
adjusting the pH value of the solution to 6-7 to make the solution acidic, adding a surface treatment agent for stirring reaction for 12-48 h, and assembling the strip-shaped nanoparticles into hollow nanoparticle micelles; and
and adjusting the pH value of the solution to 8-9 to make the solution alkaline and stirring to prevent further assembly of the hollow nanoparticle micelles.
5. The method as claimed in claim 2, wherein the stirring reaction time of the nano-bonding agent in the reaction kettle is set to 24-96 h.
6. The method according to claim 1 or 2, wherein the alcohol solution is selected from one or more of ethanol, isopropanol, methanol, butanol and propanol, wherein the weight ratio of the surface treatment agent to the nanoparticles is 0.1-10% and 5-30%, respectively, and the balance is alcohol.
7. The method of claim 1 or 2, wherein the surface treatment agent comprises the following components in parts by weight:
1-8% of polyethylene oxide or polyvinyl ether;
tartaric acid or salicylic acid 0.5-2.5%;
threonine or isoleucine 0.05-0.5%;
the balance being toluene.
8. The method according to claim 1 or 2, wherein the material of the nano particles is selected from one or more of titanium dioxide, silicon dioxide and aluminum oxide, and the particle diameter of the nano particles is 5nm to 50 nm;
the shape of the assembled hollow nano particle micelle is one or more of a hollow square, a hollow rhombus, a hollow pentagon, a hollow hexagon and a circular ring, the wall thickness of the hollow nano particle micelle is 100 nm-2000 nm, and the size of the hole is 300 nm-20000 nm.
9. The method of claim 2, wherein the weight ratio of each component is as follows:
0.05-0.2% of water-based flatting agent, 0.03-0.3% of water-based dispersant, 0.06-0.6% of water-based thickener, 0.02-0.2% of water-based defoamer, 0.04-0.4% of water-based film-forming agent, 0.05-12% of nano bonding agent, 0.1-20% of hollow nano particle micelle and the balance of deionized water.
10. The method of claim 2, wherein the nano-bonding agent comprises the following components in weight ratio:
5-30% of modified acrylate or modified polyurethane;
acetic acid or oxalic acid 0.5-2%;
0.05 to 0.5 percent of silane coupling agent;
1-2.5% of silanol and 0.7-3% of glycol or glycerol;
0.5 to 2.5 percent of curing agent;
the balance of ethanol or deionized water.
11. The method according to claim 10, wherein the silane coupling agent is selected from one or more of KH550, KH560, KH 570.
12. A superhydrophilic coating prepared according to the method of any one of claims 1-11.
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