CN112175455A - Super-hydrophobic self-cleaning coating material and preparation method thereof - Google Patents
Super-hydrophobic self-cleaning coating material and preparation method thereof Download PDFInfo
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Abstract
The invention is suitable for the technical field of super-hydrophobic coating preparation, and provides a super-hydrophobic self-cleaning coating material and a preparation method thereof, wherein the method comprises the following steps: firstly, adding 3-8 parts by weight of polystyrene resin into 80-97 parts by weight of butyl acetate solvent, after uniform dispersion, sequentially adding nano filler, anti-settling agent and curing agent, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A; by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions of CATB and CATC is 0.1mol and the molar ratio of bismuth element to halogen element is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres; adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating; coating the prepared super-hydrophobic self-cleaning coating on a substrate to form a coating; by utilizing the photocatalysis characteristic, the super-hydrophobic self-cleaning effect is greatly improved.
Description
Technical Field
The invention belongs to the technical field of super-hydrophobic coating preparation, and particularly relates to a super-hydrophobic self-cleaning coating material and a preparation method thereof.
Background
In recent years, self-cleaning coatings have received a great deal of attention. The super-hydrophobic (water contact angle is larger than 150 degrees) self-cleaning coating takes away dust through water drop rolling, and the self-cleaning function similar to that of lotus leaves is realized. However, in the actual air environment, the pollutants are various, including not only hydrophilic dust pollutants, but also lipophilic organic pollutants, including solid pollutants, liquid pollutants, and mixtures of various pollutants, and the existing superhydrophobic coating cannot effectively remove all the pollutants with different characteristics, so that in the actual use process, the superhydrophobic characteristic of the coating is lost due to the continuous accumulation of the pollutants, and in addition, the superhydrophobic characteristic of the coating is gradually lost due to mechanical friction, weather aging and other reasons. Therefore, the existing super-hydrophobic coating still has the problem of short actual service time.
The superhydrophobic coatings disclosed in the prior art have some problems, such as: the preparation method is complex, special equipment is often needed, the process is complicated, the selectivity is realized on a base material, the method is not suitable for preparing a super-hydrophobic coating in a large area, and the super-hydrophobic durability of the coating is poor, so that the self-cleaning function life of the coating is short, the improvement of the surface roughness of a matrix by a micro-nano composite structure formed by self-assembly of nano particles is limited, and the size and arrangement of a self-assembly body forming the micro-nano composite structure are not controllable.
Therefore, the super-hydrophobic self-cleaning coating still has research values of improving degradation of organic pollutants, super-hydrophobicity and self-cleaning.
Disclosure of Invention
The embodiment of the invention provides a super-hydrophobic self-cleaning coating material, aiming at solving the problems of the existing super-hydrophobic self-cleaning coating.
The embodiment of the invention is realized in such a way that the preparation method of the super-hydrophobic self-cleaning coating material comprises the following steps:
s1, adding 3-8 parts by weight of polystyrene resin into 80-97 parts by weight of butyl acetate solvent, dispersing uniformly, sequentially adding nano filler, anti-settling agent and curing agent, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated substrate, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
As a further scheme of the invention: in S1, the polystyrene resin is 4-6 parts by weight, and the butyl acetate solvent is 85-95 parts by weight.
As a further scheme of the invention: in S1, the polystyrene resin is 5 parts by weight, and the butyl acetate solvent is 95 parts by weight.
As a further scheme of the invention: in S1, the nano-filler is at least one of silica, titanium dioxide or hectorite; the anti-settling agent is at least one of bentonite and kaolin; the curing agent is polyamide resin.
As a further scheme of the invention: in S2, the specific preparation method of the bismuth oxyhalide microspheres comprises: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding 25w% by mass of a cetyl trimethyl ammonium bromide (CATB) solution and a cetyl trimethyl ammonium chloride (CATC) solution into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), adding 3X 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at room temperature of 25 ℃ for 10min, filtering, washing 5 times by respectively using 50ml of ethanol and 20oml of ultrapure water, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
As a further scheme of the invention: in S2, the preparation method of the modified bismuth oxyhalide microspheres comprises: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
As a further scheme of the invention: in S4, the substrate is a glass slide or an aluminum sheet.
The embodiment of the invention also provides a super-hydrophobic self-cleaning coating material, which is prepared by the preparation method of the super-hydrophobic self-cleaning coating material.
According to the preparation method of the super-hydrophobic self-cleaning coating material provided by the embodiment of the invention, the adopted bismuth oxyhalide is a microsphere with a flower cluster structure formed by self-assembling nano-scale nano sheets, is a good micro-nano composite structure, does not need to depend on uncontrollable self-assembly among particles to form the micro-nano composite structure, is compounded with PS (polystyrene) film-forming resin after hydrophobic modification to form the super-hydrophobic self-cleaning coating material, and utilizes the photocatalysis characteristic to greatly improve the super-hydrophobic self-cleaning effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
According to the super-hydrophobic self-cleaning coating material provided by the embodiment of the invention, the adopted bismuth oxyhalide is a microsphere with a flower cluster structure formed by self-assembling nano-sheets, and is a good micro-nano composite structure, the micro-nano composite structure is formed without depending on uncontrollable self-assembly among particles, the super-hydrophobic self-cleaning coating material is formed by compounding hydrophobic modified particles and PS film-forming resin, and the super-hydrophobic self-cleaning coating material is prepared by utilizing the photocatalysis characteristic, so that the super-hydrophobic self-cleaning effect is greatly improved.
The embodiment of the invention provides a preparation method of a super-hydrophobic self-cleaning coating material, which comprises the following steps:
s1, adding 3-8 parts by weight of polystyrene resin into 80-97 parts by weight of butyl acetate solvent, dispersing uniformly, sequentially adding nano filler, anti-settling agent and curing agent, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated substrate, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
A large number of experiments prove that nano particles with ultraviolet catalytic activity and common structures, such as nano titanium dioxide and nano zinc oxide, are self-assembled to form a micro-nano structure, and then the micro-nano structure and a cross-linked film-forming matrix with low surface energy form a super-hydrophobic self-cleaning coating. Because the ultraviolet light only accounts for 5 percent of the sunlight, the utilization of the material with photocatalytic activity to the sunlight in the nature is severely limited, and the common inorganic nano material has poor dispersibility due to small particle size and large specific surface area, and is easy to form assemblies with different sizes, thereby not only seriously influencing the exertion of the photocatalytic activity, but also causing different super-hydrophobic self-cleaning degrees of different areas of the coating; the bismuth semiconductor material has good visible light photocatalytic activity, so that the bismuth oxyhalide synthesized by the binary solvent method is a microsphere with a flower cluster structure formed by self-assembly of nano-scale nano sheets, is a good micro-nano composite structure, does not need to form the micro-nano composite structure by uncontrollable self-assembly among particles, is compounded with PS (polystyrene) film-forming resin to form a super-hydrophobic self-cleaning coating material, and greatly improves the super-hydrophobic self-cleaning effect by utilizing the photocatalytic characteristic.
In the embodiment of the invention, 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate are added into a 250ml round-bottom flask, stirred at room temperature for 20min to obtain a uniform and transparent solution, cetyl trimethyl ammonium bromide (CATB) and cetyl trimethyl ammonium chloride (CATC) solutions with the mass fraction of 25w percent are added into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), 3X 10-4mol of 1 sodium borohydride and 20ml of ethanol are added into the solution, the solution is stirred at the room temperature of 25 ℃ for 10min and then filtered, the solution is respectively washed with 50ml of ethanol and 20oml of ultrapure water for 5 times, the solution is dried in vacuum at the temperature of 60 ℃ for 24h, grinding is carried out to obtain bismuth oxyhalide microspheres with a micro-nano composite structure, 4g of bismuth oxyhalide microspheres are mixed with 40ml of n-hexane, the suspension is uniformly dispersed and stirred for 30min, then 1g of low-surface-energy hydrophobic modifier perfluorotetradecyltriethoxysilane (FAS) is, and continuously stirring for 2h, vacuum drying for 24h at 60 ℃, and grinding to obtain the modified bismuth oxyhalide microspheres, so that the hydrophobicity is improved.
The embodiment of the invention also provides a super-hydrophobic self-cleaning coating material, which is prepared by the preparation method of the super-hydrophobic self-cleaning coating material.
The technical solution and the technical effect of the present invention will be further described by specific examples.
Examples 1,
The super-hydrophobic self-cleaning coating material provided by the embodiment of the invention is prepared by the following steps:
s1, adding 3 parts by weight of polystyrene resin into 80 parts by weight of butyl acetate solvent, dispersing uniformly, sequentially adding silicon dioxide, bentonite and polyamide resin, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated glass slide, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
Specifically, in S2, the specific preparation method of the bismuth oxyhalide microspheres includes: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding a solution of 25w% by mass of cetyltrimethyl ammonium bromide (CATB) and cetyltrimethyl ammonium chloride (CATC) into the solution while stirring (the molar ratio of the added bismuth nitrate to the halogen element is 1:1), and adding 3 × 10-4Stirring 1mol sodium borohydride and 20ml ethanol at 25 ℃ and room temperature for 10min, filtering, washing with 50ml ethanol and 20oml ml ultrapure water for 5 times, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
Specifically, in S2, the preparation method of the modified bismuth oxyhalide microsphere includes: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
Examples 2,
The super-hydrophobic self-cleaning coating material provided by the embodiment of the invention is prepared by the following steps:
s1, adding 3 parts by weight of polystyrene resin into 97 parts by weight of butyl acetate solvent, dispersing uniformly, sequentially adding titanium dioxide, kaolin and polyamide resin, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated glass slide, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
Specifically, in S2, the specific preparation method of the bismuth oxyhalide microspheres includes: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding 25w% by mass of a cetyl trimethyl ammonium bromide (CATB) solution and a cetyl trimethyl ammonium chloride (CATC) solution into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), adding 3X 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at room temperature of 25 ℃ for 10min, filtering, washing 5 times by respectively using 50ml of ethanol and 20oml of ultrapure water, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
Specifically, in S2, the preparation method of the modified bismuth oxyhalide microsphere includes: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
Examples 3,
The super-hydrophobic self-cleaning coating material provided by the embodiment of the invention is prepared by the following steps:
s1, adding 8 parts by weight of polystyrene resin into 80-97 parts by weight of butyl acetate solvent, dispersing uniformly, sequentially adding silicon dioxide, kaolin and polyamide resin, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated glass slide, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
Specifically, in S2, the specific preparation method of the bismuth oxyhalide microspheres includes: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding 25w% by mass of a cetyl trimethyl ammonium bromide (CATB) solution and a cetyl trimethyl ammonium chloride (CATC) solution into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), adding 3X 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at room temperature of 25 ℃ for 10min, filtering, washing 5 times by respectively using 50ml of ethanol and 20oml of ultrapure water, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
Specifically, in S2, the preparation method of the modified bismuth oxyhalide microsphere includes: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
Examples 4,
The super-hydrophobic self-cleaning coating material provided by the embodiment of the invention is prepared by the following steps:
s1, adding 8 parts by weight of polystyrene resin into 97 parts by weight of butyl acetate solvent, dispersing uniformly, sequentially adding hectorite, bentonite and polyamide resin, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated glass slide, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
Specifically, in S2, the specific preparation method of the bismuth oxyhalide microspheres includes: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding 25w% by mass of a cetyl trimethyl ammonium bromide (CATB) solution and a cetyl trimethyl ammonium chloride (CATC) solution into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), adding 3X 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at room temperature of 25 ℃ for 10min, filtering, washing 5 times by respectively using 50ml of ethanol and 20oml of ultrapure water, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
Specifically, in S2, the preparation method of the modified bismuth oxyhalide microsphere includes: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
Examples 5,
The super-hydrophobic self-cleaning coating material provided by the embodiment of the invention is prepared by the following steps:
s1, firstly, adding 4 parts by weight of polystyrene resin into 85 parts by weight of butyl acetate solvent, after uniform dispersion, sequentially adding titanium dioxide, bentonite and polyamide resin, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated glass slide, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
Specifically, in S2, the specific preparation method of the bismuth oxyhalide microspheres includes: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding 25w% by mass of a cetyl trimethyl ammonium bromide (CATB) solution and a cetyl trimethyl ammonium chloride (CATC) solution into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), adding 3X 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at room temperature of 25 ℃ for 10min, filtering, washing 5 times by respectively using 50ml of ethanol and 20oml of ultrapure water, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
Specifically, in S2, the preparation method of the modified bismuth oxyhalide microsphere includes: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
Examples 6,
The super-hydrophobic self-cleaning coating material provided by the embodiment of the invention is prepared by the following steps:
s1, firstly, adding 6 parts by weight of polystyrene resin into 95 parts by weight of butyl acetate solvent, after uniform dispersion, sequentially adding hectorite, bentonite and polyamide resin, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated glass slide, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
Specifically, in S2, the specific preparation method of the bismuth oxyhalide microspheres includes: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding 25w% by mass of a cetyl trimethyl ammonium bromide (CATB) solution and a cetyl trimethyl ammonium chloride (CATC) solution into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), adding 3X 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at room temperature of 25 ℃ for 10min, filtering, washing 5 times by respectively using 50ml of ethanol and 20oml of ultrapure water, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
Specifically, in S2, the preparation method of the modified bismuth oxyhalide microsphere includes: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
Example 7,
S1, firstly, adding 5 parts by weight of polystyrene resin into 95 parts by weight of butyl acetate solvent, after uniform dispersion, sequentially adding silicon dioxide, kaolin and polyamide resin, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, uniformly coating the prepared super-hydrophobic self-cleaning coating on the surface of the treated glass slide, then carrying out blade coating on a wire rod, drying and curing at room temperature for 1 hour, then carrying out secondary coating, and drying and curing at room temperature to finish the preparation process of the coating.
Specifically, in S2, the specific preparation method of the bismuth oxyhalide microspheres includes: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding 25w% by mass of a cetyl trimethyl ammonium bromide (CATB) solution and a cetyl trimethyl ammonium chloride (CATC) solution into the solution while stirring (the molar ratio of the added bismuth nitrate to halogen elements is 1:1), adding 3X 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at room temperature of 25 ℃ for 10min, filtering, washing 5 times by respectively using 50ml of ethanol and 20oml of ultrapure water, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
Specifically, in S2, the preparation method of the modified bismuth oxyhalide microsphere includes: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of low-surface-energy hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS), continuing stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
The contact angles and the rolling angles of the coatings of examples 1 to 7 were measured with respect to water, respectively, to obtain Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Contact angle ° | 155 | 155 | 154 | 153 | 156 | 156 | 155 |
| Angle of roll ° | 4 | 4 | 3 | 3 | 4 | 5 | 3 |
As can be seen from Table 1, the contact angle of the coating is more than 150 degrees, the rolling angle is less than 10 degrees, the hardness is more than or equal to 9H, and the visible light transmittance is more than 90 percent. Therefore, the coating material provided by the invention can be used as a super-hydrophobic self-cleaning material.
Comparative examples 1,
The comparative example is a blank, no material was applied to the substrate slide, and only a cleaning treatment was performed.
Comparative examples 2,
This comparative example differs from example 4 above only in that: the step of S1 is inconvenient, S2 and S3 are omitted, and mixture A is smeared on the substrate slide.
Comparative examples 3,
This comparative example differs from example 4 above only in that: omitting S2 and S3, adding 4g of nano ZnO, TiO2Respectively mixing with 40ml of n-hexane, stirring for 30min to obtain uniformly dispersed suspension, adding lg hydrophobic modifier perfluorotetradecyl triethoxysilane (FAS) with low surface energy, stirring for 2h, vacuum drying at 60 deg.C for 24h, and grinding to obtain hydrophobic nano ZnO and hydrophobic nano TiO2Hydrophobic nano ZnO and hydrophobic nano TiO2Adding the mixture into the mixed solution A, magnetically stirring the mixture for lh at room temperature to obtain a coating, and smearing the coating on a substrate glass slide.
The contact angles to water and the rolling angles of the coatings of comparative examples 1 to 3 were measured, respectively, to obtain table 2.
TABLE 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Contact angle ° | 20 | 94 | 155 |
| Angle of roll ° | 130 | 102 | 4 |
From the comparison of tables 1 and 2, it can be seen that the coatings of the PS resins of example 4 and comparative example 3 both satisfy the superhydrophobic property compared to the blank of comparative example and comparative example 2.
And then taking four same substrate glass slides, respectively smearing the four substrate glass slides by using the coatings of the embodiment 4, the comparison example 1, the comparison example 2 and the comparison example 3 according to the smearing method of the embodiment 4, respectively dripping a certain amount of rhodamine B/ethanol solution on the four glass slides after drying for 2 hours at room temperature to enable the coating to turn red, and measuring the color conditions of the coating surface at different time ends under the irradiation of visible light to obtain the table 3.
TABLE 3
It can be seen from table 4 that the super-hydrophobic self-cleaning coating in example 4 has better photocatalytic degradation activity for organic matters such as rhodamine B dye and the like, and can realize the self-cleaning effect of the organic matters degraded on the surface of the coating, and the modified nanoparticles in comparative example 3 have certain photocatalytic degradation activity, but are far from the photocatalytic degradation activity of example 4.
According to the preparation method of the super-hydrophobic self-cleaning coating provided by the embodiment of the invention, the adopted bismuth oxyhalide is a microsphere with a flower cluster structure formed by self-assembling nano-sheets, is a good micro-nano composite structure, does not need to depend on uncontrollable self-assembly among particles to form the micro-nano composite structure, is compounded with PS (polystyrene) film-forming resin after hydrophobic modification to form a super-hydrophobic self-cleaning coating material, and utilizes the photocatalysis characteristic to greatly improve the super-hydrophobic self-cleaning effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a super-hydrophobic self-cleaning coating material is characterized by comprising the following steps:
s1, adding 3-8 parts by weight of polystyrene resin into 80-97 parts by weight of butyl acetate solvent, dispersing uniformly, sequentially adding nano filler, anti-settling agent and curing agent, and performing ultrasonic treatment until the resin is completely dissolved to obtain uniform mixed liquid A;
s2, by adopting a binary solvent method, ensuring that the molar total amount of two halogen source solutions including CATB and CATC is 0.1mol and the molar ratio of bismuth to halogen is 1:1, synthesizing bismuth oxyhalide microspheres, and then preparing modified bismuth oxyhalide microspheres;
s3, adding the modified bismuth oxyhalide microspheres into the mixed solution A, and magnetically stirring the mixture for lh at room temperature to obtain the super-hydrophobic self-cleaning coating for coating;
s4, coating the prepared super-hydrophobic self-cleaning coating on a substrate to form a coating.
2. The method for preparing the superhydrophobic self-cleaning coating material according to claim 1, wherein in S1, the polystyrene resin is 4-6 parts by weight, and the butyl acetate solvent is 85-95 parts by weight.
3. The method for preparing the superhydrophobic self-cleaning coating material according to claim 1, wherein in S1, the polystyrene resin is 5 parts by weight, and the butyl acetate solvent is 95 parts by weight.
4. The method of claim 1, wherein in S1, the nano filler is at least one of silica, titanium dioxide or hectorite; the anti-settling agent is at least one of bentonite and kaolin; the curing agent is polyamide resin.
5. The preparation method of the superhydrophobic self-cleaning coating material according to claim 1, wherein in S2, the specific preparation method of the bismuth oxyhalide microspheres comprises the following steps: adding 35ml of distilled water, 25ml of glacial acetic acid and 0.lmol of bismuth nitrate into a 250ml round-bottom flask, stirring at room temperature for 20min to obtain a uniform and transparent solution, adding a solution of 25w% by mass of cetyltrimethyl ammonium bromide (CATB) and cetyltrimethyl ammonium chloride (CATC) into the solution while stirring (the molar ratio of the added bismuth nitrate to the halogen element is 1:1), and adding 3 × 10-4Stirring 1mol sodium borohydride and 20ml ethanol at 25 ℃ for 10min, filtering, washing with 50ml ethanol and 20oml ml ultrapure water for 5 times, vacuum drying at 60 ℃ for 24h, and grinding to obtain the bismuth oxyhalide microspheres with the micro-nano composite structure.
6. The method for preparing the superhydrophobic self-cleaning coating material according to claim 1, wherein in S2, the modified bismuth oxyhalide microspheres are prepared by the following steps: mixing 4g of bismuth oxyhalide microspheres with 40ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, adding 1g of hydrophobic modifier with low surface energy, continuously stirring for 2h, vacuum drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.
7. The method for preparing the superhydrophobic self-cleaning coating material according to claim 1, wherein in S4, the substrate is a glass slide or an aluminum sheet.
8. The method for preparing the superhydrophobic self-cleaning coating material of claim 6, wherein the hydrophobic modifier is perfluorotetradecyltriethoxysilane (FAS).
9. The method for preparing the superhydrophobic self-cleaning coating material according to claim 1, wherein in S4, the superhydrophobic self-cleaning coating is uniformly coated on the surface of the treated substrate, then a wire rod is used for blade coating, secondary coating is carried out after drying and curing for 1h at room temperature, and then drying and curing at room temperature are carried out to complete the preparation process of the coating.
10. A super-hydrophobic self-cleaning coating material, which is characterized by being prepared by the preparation method of the super-hydrophobic self-cleaning coating material as claimed in any one of claims 1-9.
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