CN109207042B - preparation method of environment-purifying super-hydrophobic durable coating - Google Patents

preparation method of environment-purifying super-hydrophobic durable coating Download PDF

Info

Publication number
CN109207042B
CN109207042B CN201810982459.4A CN201810982459A CN109207042B CN 109207042 B CN109207042 B CN 109207042B CN 201810982459 A CN201810982459 A CN 201810982459A CN 109207042 B CN109207042 B CN 109207042B
Authority
CN
China
Prior art keywords
powder
nano tio
toluene
diisocyanate
coating
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
CN201810982459.4A
Other languages
Chinese (zh)
Other versions
CN109207042A (en
Inventor
刘丹
黄智伟
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.)
Wuhan University of Technology (WUT)
Original Assignee
Wuhan University of Technology (WUT)
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 Wuhan University of Technology (WUT) filed Critical Wuhan University of Technology (WUT)
Priority to CN201810982459.4A priority Critical patent/CN109207042B/en
Publication of CN109207042A publication Critical patent/CN109207042A/en
Application granted granted Critical
Publication of CN109207042B publication Critical patent/CN109207042B/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
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a preparation method of environment-purifying super-hydrophobic durable coating,the method comprises the following steps: s1 mixing nano TiO2Adding the powder into acetone, heating for ultrasonic dispersion, adding catalyst and nano TiO2Toluene-2, 4-diisocyanate with different mass ratios of powder, keeping the temperature, reacting for time periods under the condition of stirring, washing, filtering, drying in vacuum, and S2 obtaining toluene-2, 4-diisocyanate modified nano TiO2The powder and polyurethane ESD-530 are dispersed in a solvent mixture according to a certain proportion of , the hydrophobic coating is obtained after heating, stirring and ultrasonic dispersion for time, and S3 the obtained hydrophobic coating is coated on a substrate.

Description

preparation method of environment-purifying super-hydrophobic durable coating
Technical Field
The invention belongs to the technical field of paint preparation, and particularly relates to a preparation method of environment-purifying super-hydrophobic durable coating.
Background
The super-hydrophobic coating refers to functional coatings with ultrahigh water resistance, wherein the water contact angle is higher than 150 degrees, and the water rolling angle is smaller than 10 degrees, and the special water resistance gives the super-hydrophobic coating broad application prospects in the fields of self-cleaning, oil-water separation, anti-fog and anti-freezing, fluid drag reduction and the like, so that the simple and convenient super-hydrophobic preparation method is gradually changed into relatively simple and convenient super-hydrophobic preparation methods for constructing the super-hydrophobic coating, two factors of low surface energy materials and hierarchical roughness are indispensable for constructing the super-hydrophobic coating, so that the super-hydrophobic coating generally has the defect of mechanical abrasion resistance, and the application of the super-hydrophobic coating is greatly limited.
Furthermore, grafting of low surface energy small molecules onto nanoparticles with special functions also allows the final super-hydrophobic coating to be made multifunctional, e.g. extensively studied in recent years in TiO2The common super-hydrophobic surface of the self-repairing super-hydrophobic coating is gradually reduced in super-hydrophobicity due to the attachment of oily micromolecules such as oil stains and the like, and TiO2The specific photocatalytic performance of the material can be ensured by TiO2The super-hydrophobic coating takes the base to reduce the oil stains attached to the surface thereof under the action of ambient sunlight or ultraviolet light, thereby weighingThe super-hydrophobic function is recovered. However, this method also has a problem of durability because the small molecules grafted on the surface thereof are gradually coated with TiO after being irradiated for a long time2Is degraded by the strong photocatalytic performance of the catalyst.
In addition, the research on the self-cleaning function of the traditional super-hydrophobic coating is often stopped on the lotus effect, but in reality, pollutants in the air such as PM2.5 particles, dust, bacteria and the like are still deposited on the surface and then the pollutants are likely to cause secondary pollution in the returned air. Pollutants such as metal ions and partial organic molecules in the liquid are not captured on the traditional super-hydrophobic surface, so that the cleaning effect on the liquid is achieved.
Disclosure of Invention
The invention aims to provide methods for preparing super-hydrophobic durable coatings which can be coated on various substrates and have the capability of purifying the environment.
In order to achieve the purpose, the preparation method of the environment-purifying super-hydrophobic durable coating is characterized by comprising the following steps:
s1 mixing nano TiO2Adding the powder into acetone, heating for ultrasonic dispersion, adding catalyst and nano TiO2Toluene-2, 4-diisocyanate with different mass ratios of powder is kept at the temperature, the mixture is reacted for time periods under the condition of stirring, and the obtained product is washed, filtered, vacuum-dried to obtain the toluene-2, 4-diisocyanate modified nano TiO with different mass ratios2Powder;
s2 nanometer TiO modified by toluene-2, 4-diisocyanate2The powder and polyurethane ESD-530 are dispersed in a miscible solvent according to a certain proportion of , stirred under heating and dispersed by ultrasound for periods of time to obtain the hydrophobic coating;
s3, coating the hydrophobic coating on a substrate to obtain the super-hydrophobic coating.
According to the scheme, the nano TiO2The powder is prepared by dripping anhydrous tetrabutyl titanate into anhydrous ethanol under zero temperature condition, stirring for times, adding the obtained mixed solution into benzyl alcohol, stirring at 80-90 deg.C, reacting to obtain the final productWashing the product with anhydrous ether, centrifuging, and drying to obtain the nano TiO2And (3) powder.
According to the scheme, the heating and maintaining temperature of the steps S1 and S2 is 50-60 ℃.
According to the scheme, the miscible solvent is prepared by blending acetone and xylene in a mass ratio of 1: 2.
According to the scheme, the volume ratio of the anhydrous tetrabutyl titanate to the anhydrous ethanol is 1: 3-1: 8.
According to the scheme, the nano TiO2The particle size of the powder is 20-30 nm.
According to the scheme, in the step S1, toluene-2, 4-diisocyanate and nano TiO are mixed2The mass ratio of the powder is 1: 1-5: 1.
According to the scheme, the catalyst in the step S1 is dibutyltin dilaurate.
According to the scheme, the polyurethane ESD-530 in the step S2 is used as a binder and provided by Duterun trade (Shenzhen) Limited, and the mass fraction of the binder in the hydrophobic coating is 1-5%.
According to the scheme, in the step S2, the toluene-2, 4-diisocyanate modified nano TiO2The powder accounts for 10 to 15 percent of the mass fraction of the miscible solvent.
The invention uses polyisocyanate, toluene-2, 4-diisocyanate and nano TiO2Hydroxyl on the surface of the powder reacts to generate carbamate groups, excessive toluene-2, 4-diisocyanate reacts with N-H on the carbamate groups generated in the previous step of , kinds of particles coated by oligomers are further formed in a step, and the thickness of an oligomer coating layer can be controlled by controlling the adding amount of the toluene-2, 4-diisocyanate, so that the performance of the modified particles is changed.
Compared with the prior art, the invention has the beneficial effects that:
1) the preparation method of the coating is simple, and the method of spraying steps to prepare the film is easy to push in a large scale;
2) suitability for use with a variety of substrates;
3) the cost is low, the paint is non-toxic and harmless, and does not contain fluorine;
4) the hydrophobic coating has high hydrophobicity, the average contact angle is as high as 168 degrees, and the rolling angle is lower than 2 degrees;
5) the super-hydrophobic self-cleaning coating has extremely strong controllable ultraviolet durability, and still has super-hydrophobic self-cleaning characteristics under strong ultraviolet illumination for 30 days or placed in an external environment for 300 days;
6) the abrasive paper has good wear resistance, and can bear the friction of abrasive paper for 100cm under the pressure of a 100g weight;
7) has adsorbability to positively charged pollutants, and the adsorbability to methylene blue within 1 hour reaches 93.9 percent because of the nano TiO modified by toluene-2, 4-diisocyanate2The powder contains a large amount of oxygen atoms with lone pair electrons, so that pollutants with positive electricity are adsorbed.
Drawings
FIG. 1a in FIG. 1 shows toluene-2, 4-diisocyanate modified nano TiO in example 1 of the present invention2Two-step reaction process of powder; FIG. 1b is a molecular model of the modified product of example 1 of the present invention; FIG. 1c shows the reactants toluene-2, 4-diisocyanate and nano-TiO before and after the modification process of example 1 of the present invention2Infrared spectra of the powder and the modified product;
FIG. 2 is an image of drops of methylene blue-dyed water of example 2 of the present invention applied to a substrate of glass (top) metal (middle) paper (bottom), respectively, and a comparison of the changes in hydrophobicity after application of a coating on these substrates;
FIG. 3a is a schematic view of the lateral abrasion test of the super-hydrophobic coating of the glass substrate obtained in example 3 of the present invention; FIG. 3b is an optical image of example 3 of the present invention after repeatedly dragging 100cm total length over the tissue paper under 100g pressure without polyurethane added (left) and polyurethane added (right) coatings;
FIG. 4 is a comparison of the durability under UV illumination of the superhydrophobic coatings prepared from different proportions of the products obtained in examples 1, 2, 3 of the invention;
FIG. 5a shows the nano TiO obtained in example 1 of the present invention2Ultraviolet-visible light spectrum detected by the powder in the process of absorbing and degrading methylene blue; FIG. 5b shows modified nano TiO obtained in example 1 of the present invention2Powder TDI-TiO2(1:1) para-methyleneUltraviolet-visible light spectrum detected during the absorption degradation process of the basic blue; FIG. 5c shows modified nano TiO obtained in example 3 of the present invention2Powder TDI-TiO2(5:1) ultraviolet-visible light spectrum for detecting the absorption degradation process of methylene blue; FIG. 5d shows modified nano TiO obtained in example 4 of the present invention2Powder TDI-TiO2(5:1) ultraviolet-visible spectrum for detecting the absorption degradation process of methyl orange.
Detailed Description
For a better understanding of the present invention, reference is made to the following examples which illustrate, but are not to be construed as limited to the following examples.
ESD-530 used in the present invention is provided by Duterun trade (Shenzhen) Limited, which is a modified copolymer binder; as an adhesive precursor, the adhesive has excellent adhesiveness with the surface of a film of metal, PVC, PET and the like, has high melting point and can be applied to various coating technologies. ESD-530 can be crosslinked with NCO or various crosslinking agents to improve physicochemical properties; solid content: 100 percent; tg: 49 ℃; melting point: 125 ℃ and 135 ℃; tensile strength: 30N/mm2(ii) a Density: 1.2g/cm3(ii) a Acid value:>3mg KOH/g; hydroxyl value:<2mg KOH/g; and (3) storage: stored at room temperature for 12 months.
Example 1
1) Nano TiO 22The preparation of the powder comprises the steps of dropwise adding 2ml of anhydrous tetrabutyl titanate into 8ml of anhydrous ethanol under the zero-temperature condition, stirring for periods of time, adding the obtained mixed solution into 40ml of benzyl alcohol, stirring at 80 ℃ and continuously reacting for 9 hours, washing the obtained product with anhydrous ether according to the ratio of 1:9, centrifugally separating, repeating twice and drying to obtain the nano TiO2Powder with the grain diameter of about 25 nm;
2) toluene-2, 4-diisocyanate modified nano TiO2Preparation of powder: nano TiO obtained in the step 12Adding 400mg of the powder into 70ml of acetone, ultrasonically dispersing for half an hour at the temperature of 50 ℃, and transferring to a three-port furnaceIn a bottle, 700ul of dibutyltin dilaurate was added as a catalyst. 400mg of toluene-2, 4-diisocyanate is dissolved in 10ml of acetone, then the toluene-2, 4-diisocyanate acetone solution is slowly dripped into a three-neck flask, the reaction temperature is maintained at 50 ℃, and the reaction is carried out for 15 hours under the condition of magnetic stirring. Washing the obtained product with toluene at room temperature, centrifuging twice, transferring to a vacuum drying oven, and vacuum drying at 85 deg.C for 6 hr to obtain toluene-2, 4-diisocyanate modified nanometer TiO2Powder TDI-TiO2(1:1)；
3) Polyurethane and modified nano TiO2Preparing a powder mixed coating: and blending acetone and xylene in a mass ratio of 2:1 to prepare the miscible solvent. Taking the modified nano TiO obtained in the step 22Adding 100mg of powder and 20mg of polyurethane (ESD-530) produced by Duterun trade (Shenzhen) Limited into 2ml of the miscible solvent, magnetically stirring for 30 minutes at 50 ℃, and then ultrasonically dispersing for 1 hour to obtain the hydrophobic coating, wherein the mass of the binder in the hydrophobic coating is 1 percent of the mass of the miscible solvent, and the mass of the toluene-2, 4-diisocyanate modified nano TiO is 1 percent of the mass of the miscible solvent2The mass of the powder is 5% of the mass of the miscible agent;
4) and spraying the obtained hydrophobic coating by a spray gun with the caliber of 3mm to obtain the super-hydrophobic coating.
As shown in FIG. 1, a is toluene-2, 4-diisocyanate modified nano TiO in example 1 of the present invention2The two-step reaction process of powder, step, isocyanic acid radical in toluene-2, 4-diisocyanate and nano TiO2Hydroxyl on the surface of the powder reacts, and excessive toluene-2, 4-diisocyanate and allophanate react in the second step, so that a coating structure is formed by gradual superposition; b is a molecular model of the modified product of example 1 of the present invention, obtained by two-step reaction in FIG. 1 a; c is reactant toluene-2, 4-diisocyanate and nano TiO before and after the modification process of the embodiment 1 of the invention2The infrared spectra of the powder and the modified product show that-OOC-NH-newly formed in the reaction of step is 1713cm-1The characteristic peak of the catalyst and the newly generated-NH-CO-NH-in the second step are 1666cm-1Characteristic peak of (a); it can be shown that toluene-2, 4-diisocyanate reacts most in two stepsFinally forming an oligomer packaging structure.
As shown in fig. 4, a black trend line is a durability test of the super-hydrophobic coating prepared in example 1 of the present invention under ultraviolet irradiation, and it can be seen that the water contact angle of the coating rapidly decreases with the increase of the ultraviolet irradiation time, and the durability is poor.
As shown in FIG. 5, FIG. 5a shows the nano TiO obtained in example 1 of the present invention2The ultraviolet-visible light spectrum of the powder for detecting the absorption degradation process of methylene blue shows that the absorption of the solution is reduced by about half after the powder is stirred for 60 minutes, and figure 5b shows that the modified nano TiO obtained in the embodiment 1 of the invention2Powder TDI-TiO2(1:1) the ultraviolet-visible light spectrum detected in the absorption degradation process of methylene blue shows that after 60 minutes of stirring, the absorption of the solution is reduced by over 80 percent, which indicates that the modification process can enhance the absorption effect of the powder on the methylene blue.
Example 2
1) Nano TiO 22The preparation of the powder comprises the steps of dropwise adding 2ml of anhydrous tetrabutyl titanate into 10ml of anhydrous ethanol under the zero-temperature condition, stirring for periods, adding the obtained mixed solution into 40ml of benzyl alcohol, stirring at 85 ℃ and continuously reacting for 9 hours, washing the obtained product with anhydrous ether according to the ratio of 1:9, centrifugally separating, repeating twice and drying to obtain the nano TiO2Powder;
2) toluene-2, 4-diisocyanate modified nano TiO2Preparation of powder: nano TiO obtained in the step 12400mg of the powder was added to 70ml of acetone, the mixture was ultrasonically dispersed at 55 ℃ for half an hour and then transferred to a three-necked flask, and 700ul of dibutyltin dilaurate was added as a catalyst. 1200mg of toluene-2, 4-diisocyanate is dissolved in 10ml of acetone, then the toluene-2, 4-diisocyanate acetone solution is slowly dripped into a three-neck flask, the reaction temperature is maintained at 55 ℃, and the reaction is carried out for 12 hours under the condition of magnetic stirring. Washing the obtained product with toluene at room temperature, centrifuging twice, transferring to a vacuum drying oven, and vacuum drying at 85 deg.C for 6 hr to obtain toluene-2, 4-diisocyanate modified nanometer TiO2Powder TDI-TiO2(3:1)；
3) Polyurethane and modified nano TiO2Preparing a powder mixed coating: and blending acetone and xylene in a mass ratio of 2:1 to prepare the miscible solvent. Taking the modified nano TiO obtained in the step 22Adding 100mg of powder and 60mg of polyurethane (ESD-530) into 2ml of the mixed solvent, magnetically stirring for 30 minutes at 55 ℃, and ultrasonically dispersing for 1 hour to obtain the hydrophobic coating, wherein the mass of the binder in the hydrophobic coating is 3% of the mass of the mixed solvent, and the mass of the toluene-2, 4-diisocyanate modified nano TiO is modified2The mass of the powder is 5% of the mass of the miscible agent;
4) the obtained hydrophobic coating is sprayed on different substrates by a spray gun with the caliber of 3mm, and the super-hydrophobic coating can be obtained.
In the example 2 of the invention shown in the attached figure 2, the methylene blue dyed water drops stand on the surface of the coating layer of which the substrate is glass (upper) metal (middle) paper (lower) in an almost spherical shape, and show super-hydrophobicity, while the -side substrate which is not sprayed with the coating layer does not show super-hydrophobicity, which shows that the preparation method of the super-hydrophobic coating layer can be simply and quickly prepared on various substrate materials and has the practical application prospect of .
As shown in fig. 4, the red trend line is a durability test of the super-hydrophobic coating prepared in example 2 of the present invention under uv illumination, and it can be seen that the water contact angle of the coating decreases slowly with the increase of uv illumination time, and the durability is enhanced compared with the coating obtained in example 1.
Example 3
1) Nano TiO 22The preparation of the powder comprises dripping 2.5ml of anhydrous tetrabutyl titanate into 13ml of anhydrous ethanol under the condition of zero degree, stirring for periods of time, adding the obtained mixed solution into 40ml of benzyl alcohol, stirring at 90 ℃ and continuously reacting for 9 hours, washing the obtained product with anhydrous ether according to the proportion of 1:9, centrifugally separating, repeating twice and drying to obtain the nano TiO2Powder;
2) toluene-2, 4-diisocyanate modified nano TiO2Preparation of powder: nano TiO obtained in the step 12Adding 400mg of the powder into 70ml of acetone, and ultrasonically dispersing at 60 DEG CHalf an hour later, the mixture was transferred to a three-necked flask, and 700ul of dibutyltin dilaurate was added as a catalyst. 2000mg of toluene-2, 4-diisocyanate was dissolved in 10ml of acetone, and then the toluene-2, 4-diisocyanate acetone solution was slowly added dropwise into a three-necked flask, and the reaction temperature was maintained at 55 ℃ and the reaction was carried out for 9 hours under magnetic stirring. Washing the obtained product with toluene at room temperature, centrifuging twice, transferring to a vacuum drying oven, and vacuum drying at 85 deg.C for 6 hr to obtain toluene-2, 4-diisocyanate modified nanometer TiO2Powder TDI-TiO2(5:1)；
3) Polyurethane and modified nano TiO2Preparing a powder mixed coating: and blending acetone and xylene in a mass ratio of 1:3 to prepare the miscible solvent. Taking the modified nano TiO obtained in the step 22Adding 100mg of powder and 60mg of polyurethane (ESD-530) into 2ml of the mixed solvent, magnetically stirring for 30 minutes at 60 ℃, and ultrasonically dispersing for 1 hour to obtain the hydrophobic coating, wherein the mass of the binder in the hydrophobic coating is 3% of the mass of the mixed solvent, and the mass of the toluene-2, 4-diisocyanate modified nano TiO is modified2The mass of the powder is 5% of the mass of the miscible agent;
4) and spraying the obtained hydrophobic coating by a spray gun with the caliber of 5mm to obtain the super-hydrophobic coating.
As shown in FIG. 3, a is a schematic diagram of the transverse abrasion test of the super-hydrophobic coating of the glass substrate obtained in example 3; b is the optical image after repeatedly dragging the gauze paper for 100cm under the pressure of 100g without adding polyurethane (left) and adding polyurethane (right) into the coating. It can be shown that the mechanical wear resistance of the coating is greatly improved by adding the polyurethane adhesive.
As shown in fig. 4, a blue trend line is a durability test of the superhydrophobic coating prepared in example 3 of the present invention under ultraviolet illumination, and it can be seen that the water contact angle of the coating does not change much with the increase of the ultraviolet illumination time, and the superhydrophobic coating obtained can still maintain superhydrophobicity after being irradiated by strong ultraviolet light for 30 days. Compared with the super-hydrophobic coating prepared by the embodiment 1, 2 and 3 of the invention, the durability of the super-hydrophobic coating under ultraviolet illumination can be obtained, and the toluene-2, 4-diisocyanate and nano Ti in the modification synthesis process are increasedO2The mass ratio of the powder can greatly improve the durability of the finally obtained super-hydrophobic coating under the ultraviolet illumination condition.
FIG. 5c shows modified nano TiO obtained in example 3 of the present invention2Powder TDI-TiO2(5:1) the ultraviolet-visible light spectrum detected in the process of absorption and degradation of methylene blue shows that the absorption of the solution is reduced by over 90 percent after stirring for 60 minutes, which can show that the prepared toluene-2, 4-diisocyanate modified nano TiO2The adsorption capacity of the powder to methylene blue is positively correlated with the grafting quality of toluene-2, 4-diisocyanate.
Example 4
1) Nano TiO 22The preparation of the powder comprises dripping 2.5ml of anhydrous tetrabutyl titanate into 15ml of anhydrous ethanol under the condition of zero degree, stirring for periods of time, adding the obtained mixed solution into 40ml of benzyl alcohol, stirring at 90 ℃ and continuously reacting for 9 hours, washing the obtained product with anhydrous ether according to the proportion of 1:9, centrifugally separating, repeating twice and drying to obtain the nano TiO2Powder;
2) toluene-2, 4-diisocyanate modified nano TiO2Preparation of powder: nano TiO obtained in the step 12400mg of the powder was added to 70ml of acetone, ultrasonically dispersed at 60 ℃ for half an hour, transferred to a three-necked flask, and 700ul of dibutyltin dilaurate was added as a catalyst. 2000mg of toluene-2, 4-diisocyanate was dissolved in 10ml of acetone, and then the toluene-2, 4-diisocyanate acetone solution was slowly added dropwise into a three-necked flask, and the reaction temperature was maintained at 60 ℃ and the reaction was carried out for 9 hours under magnetic stirring. Washing the obtained product with toluene at room temperature, centrifuging twice, transferring to a vacuum drying oven, and vacuum drying at 90 deg.C for 6 hr to obtain toluene-2, 4-diisocyanate modified nanometer TiO2Powder TDI-TiO2(5:1)；
3) Polyurethane and modified nano TiO2Preparing a powder mixed coating: and blending acetone and xylene in a mass ratio of 2:1 to prepare the miscible solvent. Taking the modified nano TiO obtained in the step 22Adding 100mg of powder and 40mg of polyurethane (ESD-530) into 2ml of the miscible solvent,magnetically stirring for 30 minutes at 60 ℃, and then ultrasonically dispersing for 1 hour to obtain the hydrophobic coating, wherein the mass of the adhesive in the hydrophobic coating is 2 percent of the mass of the miscible solvent, and the toluene-2, 4-diisocyanate modified nano TiO is obtained2The mass of the powder is 5% of the mass of the miscible agent;
4) and spraying the obtained hydrophobic coating by a spray gun with the caliber of 5mm to obtain the super-hydrophobic coating.
FIG. 5d shows modified nano TiO obtained in example 4 of the present invention2Powder TDI-TiO2(5:1) ultraviolet-visible spectrum detected during absorption test of methyl orange. It can be seen that the prepared toluene-2, 4-diisocyanate modified nano TiO2The powder has no adsorption effect on methyl orange, methylene blue shows electropositivity in a solution, and methyl orange shows electronegativity, which can indicate that the adsorption of a modified product on the methylene blue is caused by charge effect, except positively charged organic micromolecules and metal ions in liquid, PM2.5, dust, bacteria and the like in air are also positively charged, so that the super-hydrophobic coating prepared by the method has the capacity of adsorbing pollutants in the air, secondary air pollution is avoided, and the super-hydrophobic self-cleaning effect is utilized, so that the aim of purifying the environment is fulfilled, and the application prospect of is wide.

Claims (8)

  1. The preparation method of the environment-purifying super-hydrophobic durable coating is characterized by comprising the following steps of:
    s1 mixing nano TiO2Adding the powder into acetone, heating for ultrasonic dispersion, adding catalyst and nano TiO2Toluene-2, 4-diisocyanate with different mass ratios of powder is kept at the temperature, the mixture is reacted for time periods under the condition of stirring, and the obtained product is washed, filtered, vacuum-dried to obtain the toluene-2, 4-diisocyanate modified nano TiO with different mass ratios2Powder; toluene-2, 4-diisocyanate and nano TiO2The mass ratio of the powder is 3: 1-5: 1; nano TiO 22The powder is prepared by dripping anhydrous tetrabutyl titanate into anhydrous ethanol at zero temperature, stirring for times, and adding the obtained mixtureStirring and reacting in benzyl alcohol at 80-90 ℃, washing the obtained product with anhydrous ether, centrifugally separating, and drying to obtain the nano TiO2Powder;
    s2 nanometer TiO modified by toluene-2, 4-diisocyanate2The powder and polyurethane ESD-530 are dispersed in a miscible solvent according to a certain proportion of , stirred under heating and dispersed by ultrasound for periods of time to obtain the hydrophobic coating;
    s3, coating the hydrophobic coating on a substrate to obtain the super-hydrophobic coating.
  2. 2. The method of claim 1, wherein the heating and maintaining temperature of step S1 is 50 ℃ to 60 ℃, and the heating temperature of step S2 is 50 ℃ to 60 ℃.
  3. 3. The method according to claim 1, wherein the miscible solvent is prepared by blending acetone and xylene at a mass ratio of 1: 2.
  4. 4. The method according to claim 2, wherein the volume ratio of the anhydrous tetrabutyl titanate to the anhydrous ethanol is 1:3 to 1: 8.
  5. 5. The method according to claim 1, wherein the nano TiO is2The particle size of the powder is 20-30 nm.
  6. 6. The method according to claim 1, wherein the catalyst in step S1 is dibutyltin dilaurate.
  7. 7. The preparation method of claim 1, wherein the polyurethane ESD-530 serving as the binder in step S2 is provided by Duterun commerce (Shenzhen) Limited, and the mass fraction of the binder in the hydrophobic coating is 1-5%.
  8. 8. The method according to claim 1, wherein the toluene-2, 4-diiso-benzene in step S2Cyanate modified nano TiO2The powder accounts for 10 to 15 percent of the mass fraction of the miscible solvent.
CN201810982459.4A 2018-08-27 2018-08-27 preparation method of environment-purifying super-hydrophobic durable coating Active CN109207042B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810982459.4A CN109207042B (en) 2018-08-27 2018-08-27 preparation method of environment-purifying super-hydrophobic durable coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810982459.4A CN109207042B (en) 2018-08-27 2018-08-27 preparation method of environment-purifying super-hydrophobic durable coating

Publications (2)

Publication Number Publication Date
CN109207042A CN109207042A (en) 2019-01-15
CN109207042B true CN109207042B (en) 2020-01-31

Family

ID=64989246

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810982459.4A Active CN109207042B (en) 2018-08-27 2018-08-27 preparation method of environment-purifying super-hydrophobic durable coating

Country Status (1)

Country Link
CN (1) CN109207042B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109943213B (en) * 2019-03-19 2020-09-04 山东科技大学 Preparation method of environment-friendly super-hydrophobic coating with high mechanical durability
CN113444434B (en) * 2021-08-11 2022-06-14 中山大学 Preparation method and application of antifouling photocatalytic coating

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838496A (en) * 2010-04-09 2010-09-22 南京工业大学 Super-hydrophobic polyurethane/oxide nanoparticle hybrid coating material and preparation method thereof
CN107446424A (en) * 2017-08-21 2017-12-08 昆明理工大电力工程技术有限公司 A kind of super-hydrophobic three-resistance coating and preparation method thereof and application method
CN107880770A (en) * 2017-11-24 2018-04-06 武汉理工大学 A kind of preparation method of environment protection multifunctional super-hydrophobic coat

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19903391A1 (en) * 1999-01-29 2000-08-03 Bayer Ag Aqueous coating agent, process for its preparation and its use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101838496A (en) * 2010-04-09 2010-09-22 南京工业大学 Super-hydrophobic polyurethane/oxide nanoparticle hybrid coating material and preparation method thereof
CN107446424A (en) * 2017-08-21 2017-12-08 昆明理工大电力工程技术有限公司 A kind of super-hydrophobic three-resistance coating and preparation method thereof and application method
CN107880770A (en) * 2017-11-24 2018-04-06 武汉理工大学 A kind of preparation method of environment protection multifunctional super-hydrophobic coat

Also Published As

Publication number Publication date
CN109207042A (en) 2019-01-15

Similar Documents

Publication Publication Date Title
Huang et al. Environmentally durable superhydrophobic surfaces with robust photocatalytic self-cleaning and self-healing properties prepared via versatile film deposition methods
CN113604095B (en) Porous powder loaded with super-hydrophobic particles and preparation method and application thereof
Fu et al. Robust liquid-repellent coatings based on polymer nanoparticles with excellent self-cleaning and antibacterial performances
CN109370408B (en) Method for preparing super-hydrophobic coating by compounding waterborne polyurethane and hydrophobic modified inorganic nanoparticles
CN112831241A (en) Super-hydrophobic and super-oleophobic epoxy resin coating and preparation method thereof
Zhang et al. Room-temperature fabrication of TiO2-PHEA nanocomposite coating with high transmittance and durable superhydrophilicity
Zhao et al. Fabrication of self-healing waterbased superhydrophobic coatings from POSS modified silica nanoparticles
Chen et al. Environmental stimuli-responsive self-repairing waterbased superhydrophobic coatings
Fan et al. WO3-based slippery coatings with long-term stability for efficient fog harvesting
CN109207042B (en) preparation method of environment-purifying super-hydrophobic durable coating
US20220145084A1 (en) Improvements relating to superhydrophobic surfaces
CN108641419B (en) Super-hydrophilic coating sol and preparation and use methods thereof
CN111534162B (en) Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof
CN105820605A (en) Preparation method of universal super-amphiphobic nano coating based on flower shape titanium dioxide nano particles
CN111908480A (en) Super-amphiphobic material, preparation method thereof and preparation method of super-amphiphobic surface coating
CN115286996B (en) Super-hydrophobic organic silicon coating and preparation method and application thereof
CN108774447B (en) Preparation method of carbon-silver microsphere/epoxy resin super-hydrophobic coating
CN113372814B (en) Cage-shaped polysilsesquioxane-based super-hydrophilic functional coating and preparation method thereof
CN115074007B (en) Inorganic-organic composite super-hydrophilic coating and preparation method and application thereof
CN112143332B (en) Super-hydrophobic coating and preparation method thereof
JP5682396B2 (en) Coating composition, superhydrophobic coating film obtained using the same, and method for producing the same
WO2022247205A1 (en) Wear-resistant, anti-ultraviolet and anti-static super-hydrophobic fabric and preparation method therefor
US20190262490A1 (en) Composite particles, dispersion liquid, film, deodorizing material, wet wiper, and spray
CN110964426A (en) Ultraviolet-resistant vehicle paint and preparation method thereof
CN115197614A (en) Waterproof anticorrosive paint for concrete and preparation method thereof

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