CN114574086B - Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof - Google Patents

Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof Download PDF

Info

Publication number
CN114574086B
CN114574086B CN202210260190.5A CN202210260190A CN114574086B CN 114574086 B CN114574086 B CN 114574086B CN 202210260190 A CN202210260190 A CN 202210260190A CN 114574086 B CN114574086 B CN 114574086B
Authority
CN
China
Prior art keywords
coating
self
hydrophobic
super
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210260190.5A
Other languages
Chinese (zh)
Other versions
CN114574086A (en
Inventor
范倩倩
温璐
卫思颖
马建中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN202210260190.5A priority Critical patent/CN114574086B/en
Publication of CN114574086A publication Critical patent/CN114574086A/en
Application granted granted Critical
Publication of CN114574086B publication Critical patent/CN114574086B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/16—Esters of inorganic acids
    • C09D101/18—Cellulose nitrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D189/00—Coating compositions based on proteins; Coating compositions based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a self-cleaning coating with super-hydrophobic and photocatalytic functions and a preparation method thereof, belongs to the technical field of functional coatings, combines the super-hydrophobic function and the photocatalytic function, and solves the problems that the existing self-cleaning coating is low in cleaning efficiency and cannot clean water and oil two-phase dirt simultaneously. The invention discloses a preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions, which comprises the steps of firstly priming a high-molecular film-forming agent and then coating nano TiO 2 Perovskite nanocrystalline composite material and low surface energy substance solution; compared with the traditional self-cleaning coating, the self-cleaning coating with the super-hydrophobic and photocatalytic functions has the advantages of high self-cleaning efficiency, strong practicability and the like and has the photocatalytic function and the hydrophobic function at the same time.

Description

Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof
Technical Field
The invention belongs to the technical field of functional coatings, and particularly relates to a self-cleaning coating with super-hydrophobic and photocatalytic functions and a preparation method thereof.
Background
The super-hydrophobic self-cleaning coating is a coating with a contact angle of the surface of the coating to water of more than 150 degrees and a rolling angle of less than 10 degrees. When water drops fall on the surface of the super-hydrophobic self-cleaning coating and take away attachments such as dust and the like on the surface, the super-hydrophobic self-cleaning coating has the characteristics of self-cleaning and adhesion resistance. However, such coatings only have a self-cleaning effect on aqueous dirt, and are not universal, limiting their further applications.
TiO 2 The material is used as a photocatalytic material and is widely applied to sewageThe degradation treatment of the dye can effectively degrade most pollutants. Therefore, in recent years, tiO has been used 2 The research of constructing the photocatalytic self-cleaning coating is concerned by introducing the photocatalytic self-cleaning coating into the coating. But conventional TiO 2 The self-cleaning coating has the problems of low self-cleaning efficiency, low visible light utilization rate and the like. Adding TiO into the mixture 2 The composite material with better photocatalysis performance can be obtained by compounding the material with perovskite nanocrystalline. However, the perovskite material has poor water resistance and stability, and the commercial application of the perovskite material is restricted.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a self-cleaning coating with super-hydrophobic and photocatalytic functions and a preparation method thereof, wherein the super-hydrophobic and photocatalytic functions are combined to overcome the defects that the existing self-cleaning coating is low in cleaning efficiency and cannot simultaneously clean water and oil two-phase dirt.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions, which comprises the following steps:
step 1: coating a macromolecular film-forming agent on the surface of a substrate, and drying to obtain the substrate with a base coating;
and 2, step: mixing nanometer TiO 2 Coating the perovskite nano-crystalline composite dispersion liquid on the surface of the substrate with the base coating, drying, fusing and curing to obtain the substrate with the pretreatment coating;
and 3, step 3: coating a low surface energy substance solution on the surface of the substrate with the pretreatment coating, drying, curing, and forming a film to finally obtain the self-cleaning coating with the super-hydrophobic and photocatalytic functions.
Further, in the step 1, a spray gun is used for coating the polymer film-forming agent on the surface of the substrate; in the step 2 and the step 3, the coating mode is spray gun coating, spin coating, dipping or deposition.
Further, in the step 1, the drying is carried out for 0.5 to 5 hours at room temperature; in the step 2, the drying is carried out for 0.5 to 5 hours at the temperature of between 50 and 90 ℃; in the step 3, the drying is carried out for 2 to 12 hours at the temperature of between 25 and 120 ℃.
Further, in step 1, the substrate comprises leather, synthetic leather, fabric, paper, plastic, metal, ceramic or glass.
Further, in step 1, the polymer film forming agent comprises casein, acrylic resin, polyurethane, chitosan, zein, gelatin, nitrocellulose or epoxy resin; the solid content of the macromolecular film-forming agent is 20-40%, and the coating dosage of the macromolecular film-forming agent is 0.3-1.2 ml/cm 2 。
Further, in step 2, the nano TiO 2 The preparation method of the perovskite nano-crystalline composite material dispersion liquid comprises the following steps: mixing nanometer TiO 2 The perovskite nanocrystal and the solvent are mixed according to the volume ratio of (1-30) g: (5-20) g: (100-600) L, and after uniform mixing, obtaining the nano TiO 2 Perovskite nanometer crystal composite material dispersion liquid.
Further, the solvent includes ethanol, isopropanol, methanol or n-hexane; the perovskite nanocrystal comprises CaTiO 3 、APbX 3 、A 3 Bi 2 X 9 、Cs 2 AgBX 6 Or Cs 2 NaBX 6 Form (I) wherein A = CH 3 NH 3 + 、CH(NH 2 ) 2 + Cs, B = Bi, in or Sb, X = Cl, br or I; and (3) uniformly mixing by adopting ultrasonic stirring, wherein the ultrasonic stirring time is 5-60 min.
Further, in step 2, the nano TiO 2 The coating amount of the perovskite nano-crystalline composite material dispersion liquid is 0.2-2.8 ml/cm 2 (ii) a In step 3, the coating amount of the low surface energy substance solution is 0.1-3.5 ml/cm 2 。
Further, in step 3, the preparation method of the low surface energy substance solution is as follows: mixing a low-surface-energy substance and a solvent according to a mass ratio of (0.2-1) g: (19.98-100) g, and mixing to obtain a low surface energy substance solution; wherein the low surface energy material comprises polytetrafluoroethylene, polydimethylsiloxane or hexadecyltrimethoxysilane; the solvent comprises tetrahydrofuran, ethanol, n-hexane or cyclohexane.
The invention also discloses the self-cleaning coating with the super-hydrophobic and photocatalytic functions, which is prepared by the preparation method of the self-cleaning coating with the super-hydrophobic and photocatalytic functions.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions, which comprises the steps of priming a high-molecular film-forming agent and then coating nano TiO 2 Perovskite nanocrystalline composite material and low surface energy substance solution. The micro-nano rough structure is constructed by using the inorganic composite photocatalytic material, and meanwhile, a low-surface-energy substance is introduced, so that the hydrophobic function of the coating is enhanced, the stability of perovskite components is improved, the service life of the perovskite components is prolonged, the obtained coating has more efficient, stable and lasting self-cleaning performance, and the coating has the function of cleaning water and oil two-phase dirt.
The invention also discloses the self-cleaning coating with super-hydrophobic and photocatalytic functions prepared by the preparation method, and the self-cleaning coating adopts TiO 2 The perovskite nanocrystalline composite material is a photocatalytic material, the introduced low surface energy substances can not only endow the coating with a hydrophobic function, but also improve the stability of perovskite components and prolong the service life of the perovskite components, and compared with the traditional self-cleaning coating, the self-cleaning coating with the super-hydrophobic and photocatalytic functions has the advantages of high self-cleaning efficiency, strong practicability and the like.
Drawings
FIG. 1 is a contact angle test chart of a self-cleaning coating with super-hydrophobic and photocatalytic functions prepared in example 2;
FIG. 2 is a graph showing the self-cleaning effect of the self-cleaning coating with superhydrophobic and photocatalytic functions prepared in example 1 and a comparative coating in the absence of light;
FIG. 3 is a graph showing the self-cleaning effect of the self-cleaning coating with super-hydrophobic and photocatalytic functions prepared in example 1 and a comparative coating when the coating is irradiated for 2.5 h.
Wherein a-example 1; b-comparative coating.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
In this document, unless otherwise specified, "comprising," including, "" containing, "" having, "or similar language, shall mean" consisting of … … "and" consisting essentially of … …, "e.g.," A comprises a "shall mean" A comprises a and the other "and" A comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. Experimental procedures without specific conditions noted in the following examples, generally according to conventional conditions, or according to conditions recommended by the manufacturer. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions comprises the following steps:
step 1: the polyurethane film forming agent with the solid content of 20 percent is sprayed by a spray gun to form 0.3ml/cm 2 The dosage of the composition is coated on the surface of leather, and the leather is dried for 0.5h at room temperature to obtain a substrate with a base coat;
step 2: mixing nanometer TiO 2 、Cs 2 AgBiBr 6 And isopropanol in a volume ratio of 1g:5:100L of mixing, dispersing the mixture evenly by means of ultrasonic action, wherein the ultrasonic time is 60min, and obtaining the nano TiO after even mixing 2 /Cs 2 AgBiBr 6 A perovskite nanocrystalline composite dispersion; using a spray gun to spray TiO 2 /Cs 2 AgBiBr 6 The perovskite nano-crystalline composite material dispersion liquid is 0.2ml/cm 2 The coating dosage of (A) is coated on the surface of a substrate with a primary coating, the substrate is dried for 0.5h at the temperature of 50 ℃, and fusion and curing are carried out to obtain the substrate with a pretreatment coating;
and 3, step 3: polytetrafluoroethylene (PDMS) and normal hexane are mixed according to the mass ratio of 0.2g:19.98g of the mixture is mixed to obtain a low surface energy substance solution; the surface of the substrate having the pretreatment coating was coated with a spray gun in an amount of 3.0ml/cm 2 Coating a low surface energy substance solution, drying for 2h at the temperature of 25 ℃, curing and forming a film to finally obtain the self-cleaning coating with super-hydrophobic and photocatalytic functions.
Example 2
A preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions comprises the following steps:
step 1: the acrylic resin with the solid content of 25 percent is formed into a film by a spray gun with the film thickness of 0.5ml/cm 2 The dosage of the composition is coated on the surface of the synthetic leather, and the synthetic leather is dried for 2 hours at room temperature to obtain a substrate with a bottom coating;
and 2, step: mixing nanometer TiO 2 、CaTiO 3 The perovskite nanocrystal and ethanol are mixed according to the volume ratio of 20g:20: mixing at 600L, dispersing uniformly by ultrasonic action for 40min to obtain nanometer TiO 2 /CaTiO 3 A perovskite nanocrystalline composite dispersion; tiO is coated by spin coating 2 /CaTiO 3 The perovskite nano-crystalline composite material dispersion liquid is 0.5ml/cm 2 The coating dosage of (A) is coated on the surface of a substrate with a primary coating, the substrate is dried for 0.5h at the temperature of 50 ℃, and fusion and curing are carried out to obtain the substrate with a pretreatment coating;
and 3, step 3: mixing polydimethylsiloxane and ethanol according to a mass ratio of 0.4g:39.96g of the mixture is mixed to obtain a low-surface-energy substance solution; the surface of the substrate with the pretreatment coating is coated by spin coating in an amount of 2.5ml/cm 2 Coating a low surface energy substance solution, drying for 5h at the temperature of 50 ℃, curing and forming a film to finally obtain the self-cleaning coating with super-hydrophobic and photocatalytic functions.
Example 3
A preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions comprises the following steps:
step 1: a spray gun is utilized to spray a casein film forming agent with the solid content of 30 percent to 1ml/cm 2 The dosage of the composition is coated on the surface of the fabric, and the fabric is dried for 5 hours at room temperature to obtain a substrate with a base coating;
step 2: mixing nanometer TiO 2 、Cs 2 NaBiCl 6 The volume ratio of the perovskite nanocrystal to methanol is 30g:20: mixing at 500L, dispersing uniformly with the help of ultrasonic action, wherein the ultrasonic time is 50min, and mixing uniformly to obtain the nano TiO 2 /Cs 2 NaBiCl 6 A perovskite nanocrystalline composite dispersion; the nano TiO 2 Perovskite nanocrystals are all commercially available grades; impregnating TiO 2 /Cs 2 NaBiCl 6 The perovskite nanocrystalline composite material is dispersed in a dispersion liquid of 2.8ml/cm 2 The coating amount of the (B) is coated on the surface of the substrate with the base coating, and the substrate is dried for 0.5h at the temperature of 90 ℃ and then fused and cured to obtain the substrate with the pretreatment coating;
and step 3: mixing hexadecyl trimethoxyl silane and ethanol according to the mass ratio of 1g:99.9g of the mixture is mixed to obtain a low surface energy substance solution; the surface of the substrate with the pretreatment coating is coated by dipping in an amount of 1.0ml/cm 2 Coating a low surface energy substance solution, drying for 10h at the temperature of 120 ℃, curing and forming a film to finally obtain the self-cleaning coating with super-hydrophobic and photocatalytic functions.
Example 4
A preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions comprises the following steps:
step 1: the chitosan with the solid content of 40 percent is formed into a film by a spray gun with the concentration of 1.2ml/cm 2 The dosage of the composition is coated on the surface of the ceramic, and the ceramic is dried for 4.5 hours at room temperature to obtain a substrate with a base coating;
step 2: nano TiO is mixed with 2 、CH(NH 2 ) 2 + PbBr 3 The volume ratio of the perovskite nanocrystal to n-hexane is 30g:20: mixing at 600L, dispersing uniformly by ultrasonic action for 60min to obtain nanometer TiO 2 A perovskite nanocrystalline composite dispersion; the nano TiO 2 Perovskite nanocrystals are all commercially available grades; impregnating TiO 2 /CH(NH 2 ) 2 + PbBr 3 The perovskite nano-crystalline composite material dispersion liquid is 1.5ml/cm 2 The coating dosage of (2) is coated on the surface of a substrate with a base coating, and the substrate is dried for 3.5 hours at the temperature of 65 ℃ and then fused and cured to obtain the substrate with a pretreatment coating;
and step 3: hexadecyl trimethoxy silane and tetrahydrofuran are mixed according to the mass ratio of 1g:88.9g of the mixture is mixed to obtain a low surface energy substance solution; the surface of the substrate with the pretreatment coating is coated by dipping in an amount of 3.5ml/cm 2 Coating a low surface energy substance solution, drying for 12h at the temperature of 120 ℃, curing and forming a film to finally obtain the self-cleaning coating with super-hydrophobic and photocatalytic functions.
Example 5
A preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions comprises the following steps:
step 1: a spray gun is utilized to form a film forming agent with the solid content of 25 percent zein by 0.8ml/cm 2 The dosage of the composition is coated on the surface of glass, and the glass is dried for 1.8 hours at room temperature to obtain a substrate with a base coating;
step 2: mixing nanometer TiO 2 、CH(NH 2 ) 2 + PbBr 3 The volume ratio of the perovskite nanocrystal to n-hexane is 15g:8:230L, uniformly dispersing the mixture by means of ultrasonic action, wherein the ultrasonic time is 5min, and uniformly mixing to obtain the nano TiO 2 /CH(NH 2 ) 2 + PbBr 3 A perovskite nanocrystalline composite dispersion; the nano TiO 2 Perovskite nanocrystals are all of the commercial grade; by depositing TiO 2 /CH(NH 2 ) 2 + PbBr 3 The perovskite nano-crystalline composite material dispersion liquid is 0.8ml/cm 2 The coating dosage of (A) is coated on the surface of a substrate with a primary coating, the substrate is dried for 2 hours at the temperature of 88 ℃, and fusion and solidification are carried out to obtain the substrate with a pretreatment coating;
and step 3: hexadecyl trimethoxy silane and cyclohexane are mixed according to the mass ratio of 0.5g:73.2g of the mixture is mixed to obtain a low surface energy substance solution; the surface of the substrate with the pretreatment coating is coated by dipping in an amount of 0.1ml/cm 2 Coating a low surface energy substance solution, drying for 8h at the temperature of 45 ℃, curing and forming a film to finally obtain the self-cleaning coating with super-hydrophobic and photocatalytic functionsAnd (3) a layer.
Example 6
A preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions comprises the following steps:
step 1: a spray gun is utilized to make the nitrocellulose with the solid content of 30 percent form a film agent of 0.8ml/cm 2 The dosage of the composition is coated on the surface of plastic, and the plastic is dried for 1.8 hours at room temperature to obtain a substrate with a base coat;
step 2: mixing nanometer TiO 2 、Cs 3 Bi 2 Cl 9 The volume ratio of the perovskite nanocrystal to n-hexane is 15g:8:230L, uniformly dispersing the mixture by means of ultrasonic action, wherein the ultrasonic time is 5min, and uniformly mixing to obtain the nano TiO 2 /Cs 3 Bi 2 Cl 9 A perovskite nanocrystalline composite dispersion; the nano TiO 2 Perovskite nanocrystals are all commercially available grades; by depositing TiO 2 /Cs 3 Bi 2 Cl 9 The perovskite nano-crystalline composite material dispersion liquid is 2.5ml/cm 2 The coating amount of the (B) is coated on the surface of a substrate with a primary coating, the substrate is dried for 3.5 hours at the temperature of 65 ℃, and fusion and curing are carried out to obtain the substrate with a pretreatment coating;
and 3, step 3: hexadecyl trimethoxy silane and cyclohexane are mixed according to the mass ratio of 0.4g:48g of the mixture is mixed to obtain a low surface energy substance solution; the surface of the substrate with the pretreatment coating is coated by dipping in an amount of 0.3ml/cm 2 Coating a low surface energy substance solution, drying for 6h at the temperature of 30 ℃, curing and forming a film to finally obtain the self-cleaning coating with super-hydrophobic and photocatalytic functions.
Fig. 1 is a contact angle test chart of the self-cleaning coating with super-hydrophobic and photocatalytic functions prepared in example 2, and it can be seen from the chart that the contact angle of the super-hydrophobic photocatalytic coating constructed in example 2 is greater than 150 ℃, WCA =154.5 °, and the super-hydrophobic coating has obvious super-hydrophobic characteristics.
Fig. 2 and fig. 3 are diagrams showing the self-cleaning effect of the self-cleaning coating with super-hydrophobic and photocatalytic functions prepared in example 1 and a comparative coating when no light is irradiated and light is irradiated for 2.5 hours, respectively, wherein leather is selected as a substrate of the coating, rhodamine B is selected as simulated dirt, and a digital camera is used for recording the change condition of the rhodamine B print on the surface of the coating under the irradiation of visible light; the comparative coating was a coating without a sprayed photocatalytic material. As can be seen from the figure, compared with the comparative sample, the color of the rhodamine B constructed on the coating surface in the example 1 is obviously lightened, which indicates that the rhodamine B has an obvious visible light self-cleaning effect.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims (5)

1. A preparation method of a self-cleaning coating with super-hydrophobic and photocatalytic functions is characterized by comprising the following steps:
step 1: coating a macromolecular film-forming agent on the surface of a substrate, and drying to obtain the substrate with a base coating;
step 2: mixing nanometer TiO 2 Coating the perovskite nano-crystalline composite dispersion liquid on the surface of the substrate with the base coating, drying, fusing and curing to obtain the substrate with the pretreatment coating;
and step 3: coating a low-surface-energy substance solution on the surface of a substrate with a pretreatment coating, drying, curing, and forming a film to finally obtain a self-cleaning coating with super-hydrophobic and photocatalytic functions;
the high-molecular film forming agent comprises casein, acrylic resin, polyurethane, chitosan, zein, gelatin, nitrocellulose or epoxy resin; the solid content of the high-molecular film forming agent is 20 to 40 percent, and the coating dosage of the high-molecular film forming agent is 0.3 to 1.2ml/cm 2 ；
The nano TiO 2 The preparation method of the perovskite nano-crystalline composite material dispersion liquid comprises the following steps: mixing nanometer TiO 2 The perovskite nanocrystal and the solvent are mixed according to the proportion of (1 to 30) g: (5 to 20) g: mixing (100 to 600) L, and mixingAfter being homogenized, nano TiO is obtained 2 A perovskite nanocrystalline composite dispersion; the nano TiO 2 The coating amount of the perovskite nano-crystalline composite material dispersion liquid is 0.2 to 2.8ml/cm 2 ；
The nano TiO 2 The solvent in the perovskite nano-crystalline composite material dispersion liquid comprises ethanol, isopropanol, methanol or normal hexane; the perovskite nanocrystal comprises CaTiO 3 、APbX 3 、A 3 Bi 2 X 9 、Cs 2 AgBX 6 Or Cs 2 NaBX 6 Type (III) wherein A = CH 3 NH 3 + 、CH(NH 2 ) 2 + Cs, B = Bi, in or Sb, X = Cl, br or I; uniformly mixing the components by ultrasonic stirring, wherein the ultrasonic stirring time is 5 to 60min
The preparation method of the low surface energy substance solution comprises the following steps: mixing a low-surface-energy substance and a solvent according to a mass ratio of (0.2 to 1) g: (19.98-100) g to obtain a low surface energy substance solution; wherein the low surface energy material comprises polytetrafluoroethylene, polydimethylsiloxane or hexadecyltrimethoxysilane;
the solvent in the low surface energy substance solution comprises tetrahydrofuran, ethanol, normal hexane or cyclohexane; the coating amount of the low surface energy substance solution is 0.1 to 3.5ml/cm 2 。
2. The method for preparing a self-cleaning coating with super-hydrophobic and photocatalytic functions as claimed in claim 1, wherein in step 1, a high molecular film forming agent is coated on the surface of a substrate by a spray gun; in the step 2 and the step 3, the coating mode is spray gun coating, spin coating, dipping or deposition.
3. The preparation method of the self-cleaning coating with the super-hydrophobic and photocatalytic functions as claimed in claim 1, wherein in step 1, the drying is performed at room temperature for 0.5 to 5 hours; in the step 2, the drying is carried out at the temperature of 50 to 90 ℃ for 0.5 to 5h; in the step 3, the drying is carried out at the temperature of 25 to 120 ℃ for 2 to 12h.
4. The method for preparing self-cleaning coating with super-hydrophobic and photocatalytic functions as claimed in claim 1, wherein in step 1, the substrate comprises leather, synthetic leather, fabric, paper, plastic, metal, ceramic or glass.
5. The self-cleaning coating with super-hydrophobic and photocatalytic functions, prepared by the method for preparing the self-cleaning coating with super-hydrophobic and photocatalytic functions as claimed in any one of claims 1~4.
CN202210260190.5A 2022-03-16 2022-03-16 Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof Active CN114574086B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210260190.5A CN114574086B (en) 2022-03-16 2022-03-16 Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210260190.5A CN114574086B (en) 2022-03-16 2022-03-16 Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114574086A CN114574086A (en) 2022-06-03
CN114574086B true CN114574086B (en) 2023-02-17

Family

ID=81781525

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210260190.5A Active CN114574086B (en) 2022-03-16 2022-03-16 Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114574086B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115415140A (en) * 2022-08-23 2022-12-02 泰州市创新电子有限公司 Self-cleaning method for liquid crystal display

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106862039A (en) * 2017-01-18 2017-06-20 华南理工大学 A kind of hydrophilic super-hydrophobic bipolar self-cleaning composite membrane of durability and preparation method thereof
CN108410221A (en) * 2018-04-23 2018-08-17 刘峰 Self-cleaning coating
CN109233372A (en) * 2018-08-17 2019-01-18 江苏理工学院 A kind of TiO2Acrylic resin super-hydrophobic coat and preparation method thereof
CN112457841A (en) * 2020-12-10 2021-03-09 武汉理工大学 Super-hydrophobic perovskite/silicon dioxide composite luminescent film and preparation method and application thereof
CN113372903A (en) * 2021-06-16 2021-09-10 郑州卓而泰新材料科技有限公司 Preparation method of perovskite nano composite material with core-shell structure
CN113444514A (en) * 2021-06-17 2021-09-28 上海大学 Hydrophobic perovskite-polymer composite material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106862039A (en) * 2017-01-18 2017-06-20 华南理工大学 A kind of hydrophilic super-hydrophobic bipolar self-cleaning composite membrane of durability and preparation method thereof
CN108410221A (en) * 2018-04-23 2018-08-17 刘峰 Self-cleaning coating
CN109233372A (en) * 2018-08-17 2019-01-18 江苏理工学院 A kind of TiO2Acrylic resin super-hydrophobic coat and preparation method thereof
CN112457841A (en) * 2020-12-10 2021-03-09 武汉理工大学 Super-hydrophobic perovskite/silicon dioxide composite luminescent film and preparation method and application thereof
CN113372903A (en) * 2021-06-16 2021-09-10 郑州卓而泰新材料科技有限公司 Preparation method of perovskite nano composite material with core-shell structure
CN113444514A (en) * 2021-06-17 2021-09-28 上海大学 Hydrophobic perovskite-polymer composite material and preparation method thereof

Also Published As

Publication number Publication date
CN114574086A (en) 2022-06-03

Similar Documents

Publication Publication Date Title
Yin et al. Functional and versatile colorful superhydrophobic nanocellulose-based membrane with high durability, high-efficiency oil/water separation and oil spill cleanup
CN101307210B (en) Ultra-discharging water-soluble fluor-silicon-acrylic coatings with nano particles
CN100558834C (en) A kind of green powdered paint and preparation method thereof
CN102311234B (en) Transparent self-cleaning SiO2Antifogging coating and preparation method thereof
CN114574086B (en) Self-cleaning coating with super-hydrophobic and photocatalytic functions and preparation method thereof
US20100040867A1 (en) Double layer coating, its preparation and its use for rendering ultra water-repellent and antireflective the surfaces to which it is applied
WO1995013326A1 (en) Process for the production of compounds based on silanes containing epoxy groups
CN101525504A (en) Photocatalytic self-cleaning film coating agent with self-layered isolation effect and preparation method thereof
CN112175520A (en) Preparation method and application of super-hydrophobic, transparent and durable coating
CN109651855A (en) A kind of fluorided silica nano silicon particles hydrophobing agent and its application
CN109232985A (en) Grapheme material and preparation method and application for asphalt modification
CN101538124A (en) Superhydrophilic self-cleaning SiO2Antifogging coating and preparation method thereof
CN111266277B (en) Lubricating fluid injection type super-smooth silicone rubber/nano inorganic matter dynamic hydrophobic-oleophobic hybrid coating and construction method and application thereof
CN112778885B (en) Super-hydrophobic coating material, preparation method thereof and super-hydrophobic coating
CN104087162A (en) Preparation of multi-scale micro-nano particles enhanced silicone rubber coating, and gradient coating process thereof
CN109207042B (en) preparation method of environment-purifying super-hydrophobic durable coating
CN108300328A (en) A kind of biology based waterborne coatings and preparation method thereof
CN113292876B (en) Super-hydrophobic coating and preparation method and application thereof
DE10050064A1 (en) Process for the production of fluoroalkyl functionalized silane coatings
CN111040479B (en) Method for preparing high-stability corrosion-resistant super-amphiphobic material by taking zinc oxide as material
Wang et al. Preparation of highly adhesion hydrophobic membrane and superhydrophobic membrane via electrospinning
CN114643188A (en) Method for constructing efficient visible light self-cleaning coating
WO2005014720A1 (en) Photocatalyst dispersion liquid and method for producing same
CN111004577A (en) Water-based transparent super-hydrophobic coating, preparation method and application
DE102004059152A1 (en) Coating composition, useful to prepare protecting layer and coat substrates, comprises mixture of metal- and/or semi-metal alkoxide, mixture of organosilane, fluoridated polyether, perfluoropolymer and soluble structure-viscous compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant