CN114262548A - Coating with visible light catalysis function and preparation method thereof - Google Patents
Coating with visible light catalysis function and preparation method thereof Download PDFInfo
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Abstract
A coating with a visible light catalytic function and a preparation method thereof belong to the technical field of coatings, wherein the coating with the visible light catalytic function consists of a water-based acrylic emulsion, carbon-molybdenum modified titanium dioxide powder, bismuth molybdate powder, bismuth titanate powder, a thickening agent, a dispersing agent, a leveling agent, a film-forming auxiliary agent, a wetting agent, a defoaming agent, a filler, water-based nano silicon dioxide and deionized water; the removal rate of NOx, methyl mercaptan, toluene and formaldehyde by the coating is 0.39-0.44 mu g/(m)2·s）、0.48~0.57μg/(m2·s）、0.37~0.41μg/(m2·s）、0.53~0.64μg/(m2S) respectively remove the NOx, the methyl mercaptan, the toluene and the formaldehyde by 96.7-98.3%, 97.1-98.5%, 94.9-96.8% and 98.4-99.4%.
Description
Technical Field
The invention relates to a coating with a visible light catalysis function and a preparation method thereof, belonging to the technical field of coatings.
Background
With TiO2Is a kind of photosensitive material, under the irradiation of ultraviolet or visible light, it can completely oxidize some organic pollutants into H2O、CO2And the like, and also has good effects of sterilizing and inhibiting virus activity, and simultaneously has good removal effect on gaseous pollutants, thereby becoming an ideal environment purification material.
In recent years, based on TiO2Environmental protection type coatings with photocatalytic function are continuously available. The paint is mostly multi-purpose nano-grade TiO 22After coated on the surface of the substrate, electron transition occurs under the irradiation of light, valence band electrons are excited to the conduction band and holes are generated in the valence band, oxygen and water molecules in the air are activated, and the solar cell hasActive oxygen free radicals with high reaction activity can decompose harmful gas in air and kill harmful microbe to purify environment. However, TiO in the prior art2Generally, the photocatalyst has high photocatalytic activity under the irradiation of ultraviolet light, the solar energy is mainly concentrated in the visible light range of 400-700 nanometers, and the proportion of the ultraviolet light in the sunlight is only about 4%, so that TiO in the prior art2The utilization rate of the sunlight is low in the using process, and the catalyst does not have catalytic activity particularly in the visible light range.
Chinese patent CN102702807A discloses a photocatalytic composite coating and a preparation method thereof, comprising diatomite and TiO2、C3N4、Au(OH)3And AgOH, the coating has the functions of adsorbing and visible light catalyst, can adjust indoor humidity, and better purifies indoor air. The paint prepared by the patent can only remove formaldehyde and toluene, and has no visible light catalytic degradation activity on other gas pollutants.
Chinese patent CN103756376A discloses an environment-friendly coating with a photocatalytic function and a preparation method thereof, which consists of modified nano iron oxide powder, silicate, gypsum powder, titanium dioxide, a powder anticaking agent, a curing conditioner, inorganic pigment and filler. The paint prepared by the patent can only degrade formaldehyde by photocatalysis, and the degradation removal rate of the formaldehyde is 87 percent at most.
As can be seen from the above, the existing coating with the visible light catalysis function still has the problems of single pollutant degradation type, poor catalytic degradation performance under visible light and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a coating with a visible light catalysis function and a preparation method thereof, and the following purposes are realized: the environment-friendly coating which can catalyze and degrade various air pollutants rapidly and efficiently under visible light is prepared.
In order to realize the purpose, the invention adopts the following technical scheme:
the coating with the visible light catalysis function comprises the following specific formula in parts by weight:
40-60 parts of aqueous acrylic emulsion
3-8 parts of carbon-molybdenum modified titanium dioxide powder
1-2 parts of bismuth molybdate powder
2-5 parts of bismuth titanate powder
0.5-2 parts of thickening agent
1-2 parts of dispersant
0.1-1 part of flatting agent
0.1-1.2 parts of film-forming assistant
0.1 to 1.5 parts of wetting agent
0.1-0.4 part of defoaming agent
10-18 parts of filler
0.5-1.5 parts of water-based nano silicon dioxide
15-35 parts of deionized water;
the water-based acrylic emulsion is water-based lauryl alcohol acrylate copolymer emulsion;
the thickening agent is an ethoxy polyurethane water-soluble polymer;
the dispersant is methoxy polyethylene glycol ether sodium salt;
the leveling agent is aliphatic waterborne polyurethane;
the film-forming additive is dodecyl alcohol ester;
the wetting agent is polyether and dimethyl siloxane graft copolymer;
the defoaming agent is modified polydimethylsiloxane;
the filler is one of calcium carbonate and talcum powder, and the particle size is 800-1100 meshes;
adding triethanolamine and glycerol into an organic acid aqueous solution, then adding molybdate, stirring and dissolving to obtain a solution A, adding sodium fluosilicate into a titanyl sulfate aqueous solution, dissolving completely to obtain a solution B, then pouring the solution A into the solution B, stirring strongly for 30-60 minutes, transferring into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 10-16 hours at 180-250 ℃, cooling to room temperature, filtering the reaction solution, filtering the filtered powder, and washing and drying to obtain the carbon-molybdenum modified titanium dioxide powder;
the organic acid aqueous solution is one of 1,3, 5-benzene tricarboxylic acid aqueous solution, oxalic acid aqueous solution and phenyl hexacarboxylic acid aqueous solution;
in the organic acid aqueous solution, the mass concentration of the organic acid is 10-30 wt%;
the mass ratio of the organic acid aqueous solution to the triethanolamine to the glycerol is 50-80: 1-10: 2-13;
the molybdate is one of ammonium molybdate and potassium molybdate;
the addition amount of the molybdate is 20-35% of the mass of the organic acid;
the mass ratio of the titanyl sulfate aqueous solution to the sodium fluosilicate is 100: 1-6;
the mass concentration of the titanyl sulfate in the titanyl sulfate aqueous solution is 20-45 wt%;
the mass ratio of the solution A to the solution B is 10: 5-8;
stirring with strong force at a stirring speed of 3000-5000 rpm;
and (3) washing and drying, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 70-95 ℃ for 10-14 hours.
Dissolving bismuth sulfate and ammonium phosphomolybdate in deionized water, transferring the obtained solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 180-220 ℃ for 5-8 hours, cooling to room temperature, filtering the liquid after the reaction is finished, washing the filtrate with the deionized water for three times, and drying at 75-100 ℃ for 2-5 hours to obtain bismuth molybdate powder;
the mass ratio of the bismuth sulfate to the ammonium phosphomolybdate to the deionized water is 7-18: 10-33: 150-220.
Dissolving ammonium fluotitanate in a mixed solution of deionized water and an alcohol ether solvent, stirring and controlling the temperature, adding an acidified bismuth salt aqueous solution into the mixed solution, adding an alcohol hydrothermal auxiliary agent to obtain a reaction solution, adjusting the pH of the reaction solution to 8-10 with an alkali solution, transferring the reaction solution into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, carrying out centrifugal separation, washing with water and ethanol for multiple times, and carrying out vacuum drying to obtain bismuth titanate powder;
the alcohol ether solvent is one of diethylene glycol butyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether;
the bismuth salt aqueous solution is one of a bismuth sulfate aqueous solution, a bismuth nitrate aqueous solution and a bismuth chloride aqueous solution;
the preparation method of the acidified bismuth salt aqueous solution comprises the steps of adjusting the pH of a bismuth sulfate aqueous solution to 3-5 by using sulfuric acid, adjusting the pH of a bismuth nitrate aqueous solution to 3-5 by using nitric acid, or adjusting the pH of a bismuth chloride aqueous solution to 3-5 by using hydrochloric acid;
the mass concentration of bismuth salt in the bismuth salt aqueous solution is 8-20 wt%;
the alcohol hydrothermal auxiliary agent is one of glycerol, glycol and pentaerythritol;
the alkali liquor is one of sodium hydroxide aqueous solution or ammonia water;
the mass ratio of the ammonium fluotitanate to the deionized water to the alcohol ether solvent to the acidified bismuth salt aqueous solution to the alcohol hydrothermal auxiliary agent is 7-18: 10-20: 8-15: 9-26: 3-7;
the stirring temperature is controlled, the stirring speed is 700-1200 rpm, and the temperature is 50-80 ℃;
the hydrothermal reaction is carried out at the temperature of 200-250 ℃ for 3-7 hours.
The preparation method of the coating comprises the following steps: according to the specific formula of the coating in parts by weight, firstly, adding the water-based acrylic emulsion and deionized water into a mixing kettle, sequentially adding the dispersing agent, the flatting agent, the film forming aid, the wetting agent and the defoaming agent at a stirring speed of 2000-4000 rpm, increasing the stirring speed to 5000-6500 rpm, sequentially and slowly adding the carbon-molybdenum modified titanium dioxide powder, the bismuth molybdate powder, the bismuth titanate powder, the water-based nano silicon dioxide, the filler and the thickening agent, continuously stirring for 2-5 hours, and discharging to obtain a coating finished product.
Compared with the prior art, the invention has the following beneficial effects:
1. the environment-friendly coating capable of quickly and efficiently catalyzing and degrading NOx, methyl mercaptan, methylbenzene and formaldehyde under the condition of visible light is prepared;
2. the prepared coating is white slurry, is free from barrier in two spraying or brushing ways, has dispersion stability of A/5, does not break emulsion in 3 cycles of low-temperature stability, is white, smooth and uniform in appearance, is dried for 0.4-0.5 hour, has no abnormality in water resistance for 35-42 days, has no abnormality in alkali resistance for 31-39 days, is more than 6770-6960 washing resistance times, and has artificial aging resistance (400 h) of 0 level;
3. the coating prepared by the invention has the removal rates of 0.39-0.44 mu g/(m) of NOx, methyl mercaptan, toluene and formaldehyde under the condition of visible light2·s）、0.48~0.57μg/(m2·s）、0.37~0.41μg/(m2·s）、0.53~0.64μg/(m2S) respectively remove the NOx, the methyl mercaptan, the toluene and the formaldehyde by 96.7-98.3%, 97.1-98.5%, 94.9-96.8% and 98.4-99.4%.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: coating with visible light catalysis function and preparation method thereof
The method comprises the following steps:
1. coating with visible light catalysis function
The specific formula of the coating comprises the following components in parts by weight:
55 parts of aqueous acrylic emulsion
6 parts of carbon molybdenum modified titanium dioxide powder
1.6 parts of bismuth molybdate powder
3.5 parts of bismuth titanate powder
1 part of thickening agent
1.5 parts of dispersant
0.7 part of leveling agent
0.8 part of film-forming assistant
0.8 part of wetting agent
0.2 part of defoaming agent
15 parts of filler
0.6 part of aqueous nanosilica
30 parts of deionized water
The water-based acrylic emulsion is water-based lauryl alcohol acrylate copolymer emulsion;
the thickening agent is an ethoxy polyurethane water-soluble polymer;
the dispersant is methoxy polyethylene glycol ether sodium salt;
the leveling agent is aliphatic waterborne polyurethane;
the film-forming additive is dodecyl alcohol ester;
the wetting agent is polyether and dimethyl siloxane graft copolymer;
the defoaming agent is modified polydimethylsiloxane;
the filler is calcium carbonate with the particle size of 900 meshes;
(1) preparation of carbon molybdenum modified titanium dioxide powder
Adding triethanolamine and glycerol into an organic acid aqueous solution, then adding molybdate, stirring and dissolving to obtain a solution A, adding sodium fluosilicate into a titanyl sulfate aqueous solution, dissolving completely to obtain a solution B, then pouring the solution A into the solution B, stirring strongly for 40 minutes, transferring into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 14 hours at 220 ℃, cooling to room temperature, filtering the reaction solution, filtering the filtered powder, and washing and drying to obtain carbon-molybdenum modified titanium dioxide powder;
the organic acid aqueous solution is 1,3, 5-benzene tricarboxylic acid aqueous solution;
in the organic acid aqueous solution, the mass concentration of the organic acid is 25 wt%;
the mass ratio of triethanolamine to glycerol in the organic acid aqueous solution is 70:7: 11;
the molybdate is ammonium molybdate;
the addition amount of the molybdate is 28 percent of the mass of the organic acid;
the mass ratio of the titanyl sulfate aqueous solution to the sodium fluosilicate is 100: 3;
the mass concentration of the titanyl sulfate in the titanyl sulfate aqueous solution is 30 wt%;
the mass ratio of the solution A to the solution B is 10: 7;
stirring with strong force at the stirring speed of 4200 rpm;
and (3) washing and drying, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 80 ℃ for 11 hours.
(2) Preparation of bismuth molybdate powder
Dissolving bismuth sulfate and ammonium phosphomolybdate in deionized water, transferring the obtained solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 200 ℃ for 7 hours, cooling to room temperature, filtering the liquid after the reaction is finished, washing the filtrate with the deionized water for three times, and drying at 85 ℃ for 4 hours to obtain bismuth molybdate powder;
the mass ratio of the bismuth sulfate to the ammonium phosphomolybdate to the deionized water is 13:20: 200.
(3) Preparation of bismuth titanate powder
Dissolving ammonium fluotitanate in a mixed solution of deionized water and an alcohol ether solvent, stirring and controlling the temperature, adding an acidified bismuth salt aqueous solution into the mixed solution, adding an alcohol hydrothermal auxiliary agent to obtain a reaction solution, adjusting the pH of the reaction solution to 9 with an alkali solution, transferring the reaction solution into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, carrying out centrifugal separation, washing with water and ethanol for multiple times, and then carrying out vacuum drying to obtain bismuth titanate powder;
the alcohol ether solvent is diethylene glycol monobutyl ether;
the bismuth salt aqueous solution is a bismuth sulfate aqueous solution;
the acidified bismuth salt aqueous solution is prepared by adjusting the pH of the bismuth sulfate aqueous solution to 4 with sulfuric acid;
the mass concentration of bismuth salt in the bismuth salt aqueous solution is 15 wt%;
the alcohol hydrothermal auxiliary agent is glycerol;
the alkali liquor is sodium hydroxide aqueous solution;
the mass ratio of the ammonium fluotitanate to the deionized water to the alcohol ether solvent to the acidified bismuth salt aqueous solution to the alcohol hydrothermal auxiliary agent is 13:16:12:21: 5;
the stirring temperature is controlled, the stirring speed is 950 rpm, and the temperature is 72 ℃;
the hydrothermal reaction is carried out at the temperature of 230 ℃ for 5 hours.
2. The preparation method of the coating with the visible light catalysis function comprises the following steps:
according to the specific formula of the coating in parts by weight, firstly, adding the water-based acrylic emulsion and deionized water into a mixing kettle, sequentially adding the dispersing agent, the flatting agent, the film forming aid, the wetting agent and the defoaming agent at a stirring speed of 3500 revolutions per minute, raising the stirring speed to 5500 revolutions per minute, sequentially and slowly adding the carbon-molybdenum modified titanium dioxide powder, the bismuth molybdate powder, the bismuth titanate powder, the water-based nano silicon dioxide, the filler and the thickening agent, continuously stirring for 4 hours, and discharging to obtain a finished coating.
Example 2: coating with visible light catalysis function and preparation method thereof
The method comprises the following steps:
1. coating with visible light catalysis function
The specific formula of the coating comprises the following components in parts by weight:
40 parts of aqueous acrylic emulsion
3 parts of carbon molybdenum modified titanium dioxide powder
1 part of bismuth molybdate powder
2 parts of bismuth titanate powder
0.5 part of thickening agent
1 part of dispersant
0.1 part of leveling agent
0.1 part of film-forming assistant
0.1 part of wetting agent
0.1 part of defoaming agent
10 parts of filler
0.5 part of aqueous nanosilica
15 parts of deionized water
The water-based acrylic emulsion is water-based lauryl alcohol acrylate copolymer emulsion;
the thickening agent is an ethoxy polyurethane water-soluble polymer;
the dispersant is methoxy polyethylene glycol ether sodium salt;
the leveling agent is aliphatic waterborne polyurethane;
the film-forming additive is dodecyl alcohol ester;
the wetting agent is polyether and dimethyl siloxane graft copolymer;
the defoaming agent is modified polydimethylsiloxane;
the filler is talcum powder with the particle size of 800 meshes;
(1) preparation of carbon molybdenum modified titanium dioxide powder
Adding triethanolamine and glycerol into an organic acid aqueous solution, then adding molybdate, stirring and dissolving to obtain a solution A, adding sodium fluosilicate into a titanyl sulfate aqueous solution, dissolving completely to obtain a solution B, then pouring the solution A into the solution B, stirring strongly for 30 minutes, transferring into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 10 hours at 180 ℃, cooling to room temperature, filtering the reaction solution, filtering the filtered powder, and washing and drying to obtain carbon-molybdenum modified titanium dioxide powder;
the organic acid aqueous solution is oxalic acid aqueous solution;
in the organic acid aqueous solution, the mass concentration of the organic acid is 10 wt%;
the mass ratio of the organic acid aqueous solution to the triethanolamine to the glycerol is 50:1: 2;
the molybdate is potassium molybdate;
the addition amount of the molybdate is 20 percent of the mass of the organic acid;
the mass ratio of the titanyl sulfate aqueous solution to the sodium fluosilicate is 100: 1;
the mass concentration of the titanyl sulfate in the titanyl sulfate aqueous solution is 20 wt%;
the mass ratio of the solution A to the solution B is 10: 5;
the stirring speed is 3000 r/min;
and washing and drying, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 70 ℃ for 10 hours.
(2) Preparation of bismuth molybdate powder
Dissolving bismuth sulfate and ammonium phosphomolybdate in deionized water, transferring the obtained solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 180 ℃ for 5 hours, cooling to room temperature, filtering the liquid after the reaction is finished, washing the filtrate with the deionized water for three times, and drying at 75 ℃ for 2 hours to obtain bismuth molybdate powder;
the mass ratio of the bismuth sulfate to the ammonium phosphomolybdate to the deionized water is 7:10: 150.
(3) Preparation of bismuth titanate powder
Dissolving ammonium fluotitanate in a mixed solution of deionized water and an alcohol ether solvent, stirring and controlling the temperature, adding an acidified bismuth salt aqueous solution into the mixed solution, adding an alcohol hydrothermal auxiliary agent to obtain a reaction solution, adjusting the pH of the reaction solution to 8 with an alkali solution, transferring the reaction solution into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, carrying out centrifugal separation, washing with water and ethanol for multiple times, and then carrying out vacuum drying to obtain bismuth titanate powder;
the alcohol ether solvent is propylene glycol methyl ether;
the bismuth salt aqueous solution is a bismuth nitrate aqueous solution;
the acidified bismuth salt aqueous solution is prepared by adjusting the pH of the bismuth nitrate aqueous solution to 3 with nitric acid;
the mass concentration of bismuth salt in the bismuth salt aqueous solution is 8 wt%;
the alcohol hydrothermal auxiliary agent is ethylene glycol;
the alkali liquor is ammonia water;
the mass ratio of the ammonium fluotitanate to the deionized water to the alcohol ether solvent to the acidified bismuth salt aqueous solution to the alcohol hydrothermal auxiliary agent is 7:10:8:9: 3;
the stirring temperature is controlled, the stirring speed is 700 rpm, and the temperature is 50 ℃;
the hydrothermal reaction is carried out at the temperature of 200 ℃ for 3 hours.
2. The preparation method of the coating with the visible light catalysis function comprises the following steps:
according to the specific formula of the coating in parts by weight, firstly, adding the water-based acrylic emulsion and deionized water into a mixing kettle, sequentially adding the dispersing agent, the flatting agent, the film forming aid, the wetting agent and the defoaming agent at a stirring speed of 2000 rpm, increasing the stirring speed to 5000 rpm, sequentially and slowly adding the carbon-molybdenum modified titanium dioxide powder, the bismuth molybdate powder, the bismuth titanate powder, the water-based nano silicon dioxide, the filler and the thickening agent, continuously stirring for 2 hours, and discharging to obtain a coating finished product.
Example 3: coating with visible light catalysis function and preparation method thereof
The method comprises the following steps:
1. coating with visible light catalysis function
The specific formula of the coating comprises the following components in parts by weight:
60 parts of aqueous acrylic emulsion
8 parts of carbon molybdenum modified titanium dioxide powder
2 parts of bismuth molybdate powder
5 parts of bismuth titanate powder
2 parts of thickening agent
2 parts of dispersant
1 part of leveling agent
1.2 parts of film-forming assistant
1.5 parts of wetting agent
0.4 part of defoaming agent
18 parts of filler
1.5 parts of aqueous nanosilica
35 parts of deionized water
The water-based acrylic emulsion is water-based lauryl alcohol acrylate copolymer emulsion;
the thickening agent is an ethoxy polyurethane water-soluble polymer;
the dispersant is methoxy polyethylene glycol ether sodium salt;
the leveling agent is aliphatic waterborne polyurethane;
the film-forming additive is dodecyl alcohol ester;
the wetting agent is polyether and dimethyl siloxane graft copolymer;
the defoaming agent is modified polydimethylsiloxane;
the filler is calcium carbonate with the grain size of 1100 meshes;
(1) preparation of carbon molybdenum modified titanium dioxide powder
Adding triethanolamine and glycerol into an organic acid aqueous solution, then adding molybdate, stirring and dissolving to obtain a solution A, adding sodium fluosilicate into a titanyl sulfate aqueous solution, dissolving completely to obtain a solution B, then pouring the solution A into the solution B, stirring strongly for 60 minutes, transferring into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 16 hours at 250 ℃, cooling to room temperature, filtering the reaction solution, filtering the filtered powder, and washing and drying to obtain carbon-molybdenum modified titanium dioxide powder;
the organic acid aqueous solution is phenyl hexacarboxylic acid aqueous solution;
in the organic acid aqueous solution, the mass concentration of the organic acid is 30 wt%;
the mass ratio of the organic acid aqueous solution to the triethanolamine to the glycerol is 80:10: 13;
the molybdate is potassium molybdate;
the addition amount of the molybdate is 35 percent of the mass of the organic acid;
the mass ratio of the titanyl sulfate aqueous solution to the sodium fluosilicate is 100: 6;
the mass concentration of the titanyl sulfate in the titanyl sulfate aqueous solution is 45 wt%;
the mass ratio of the solution A to the solution B is 10: 8;
the stirring speed is 5000 r/min;
and (3) washing and drying, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 95 ℃ for 14 hours.
(2) Preparation of bismuth molybdate powder
Dissolving bismuth sulfate and ammonium phosphomolybdate in deionized water, transferring the obtained solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 220 ℃ for 8 hours, cooling to room temperature, filtering the liquid after the reaction is finished, washing the filtrate with the deionized water for three times, and drying at 100 ℃ for 5 hours to obtain bismuth molybdate powder;
the mass ratio of the bismuth sulfate to the ammonium phosphomolybdate to the deionized water is 18:33: 220.
(3) Preparation of bismuth titanate powder
Dissolving ammonium fluotitanate in a mixed solution of deionized water and an alcohol ether solvent, stirring and controlling the temperature, adding an acidified bismuth salt aqueous solution into the mixed solution, adding an alcohol hydrothermal auxiliary agent to obtain a reaction solution, adjusting the pH of the reaction solution to 10 with an alkali solution, transferring the reaction solution into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, carrying out centrifugal separation, washing with water and ethanol for multiple times, and then carrying out vacuum drying to obtain bismuth titanate powder;
the alcohol ether solvent is dipropylene glycol methyl ether;
the bismuth salt aqueous solution is a bismuth chloride aqueous solution;
the acidified bismuth salt aqueous solution is prepared by adjusting the pH of a bismuth chloride aqueous solution to 5 with hydrochloric acid;
the mass concentration of bismuth salt in the bismuth salt aqueous solution is 20 wt%;
the alcohol hydrothermal auxiliary agent is pentaerythritol;
the alkali liquor is ammonia water;
the mass ratio of the ammonium fluotitanate to the deionized water to the alcohol ether solvent to the acidified bismuth salt aqueous solution to the alcohol hydrothermal auxiliary agent is 18:20:15:26: 7;
the stirring temperature is controlled, the stirring speed is 1200 rpm, and the temperature is 80 ℃;
the hydrothermal reaction is carried out at the temperature of 250 ℃ for 7 hours.
2. Preparation method of coating with visible light catalysis function
According to the specific formula of the coating in parts by weight, firstly, adding the water-based acrylic emulsion and deionized water into a mixing kettle, sequentially adding the dispersing agent, the flatting agent, the film forming aid, the wetting agent and the defoaming agent at the stirring speed of 4000 revolutions per minute, increasing the stirring speed to 6500 revolutions per minute, sequentially and slowly adding the carbon-molybdenum modified titanium dioxide powder, the bismuth molybdate powder, the bismuth titanate powder, the water-based nano silicon dioxide, the filler and the thickening agent, continuously stirring for 5 hours, and discharging to obtain a finished coating.
Comparative example 1:
on the basis of example 1, the titanium dioxide powder is not modified, and other conditions are not changed
The method comprises the following steps:
step 1, equivalently replacing carbon molybdenum modified titanium dioxide powder with titanium dioxide powder, and replacing the carbon molybdenum modified titanium dioxide powder with the titanium dioxide powder, wherein the rest of the operations are the same as those in the example 1 without preparing the carbon molybdenum modified titanium dioxide powder;
step 2 was performed as in example 1.
Comparative example 2:
on the basis of example 1, no bismuth molybdate powder was added, and the other conditions were not changed
The method comprises the following steps:
in the step 1, the bismuth molybdate powder is equivalently replaced by the carbon molybdenum modified titanium dioxide powder in the formula, the preparation of the bismuth molybdate powder is not carried out, and the rest of the operation is the same as that in the example 1;
step 2 was performed as in example 1.
Comparative example 3:
on the basis of example 1, no bismuth titanate powder was added, and the other conditions were unchanged
The method comprises the following steps:
in the step 1, the bismuth titanate powder is equivalently replaced by the carbon-molybdenum modified titanium dioxide powder in the formula, the preparation of the bismuth titanate powder is not carried out, and the rest of the operations are the same as those in the example 1;
step 2 was performed as in example 1.
And (3) performance testing:
firstly, conventional performance testing:
1. the state and the construction performance in the container are measured according to GB/T9756 and 2018;
2. the dispersion stability is determined according to GB/T5541-2017;
3. the low temperature stability is determined according to GB/T6753.3-1986;
4. the appearance of the paint film is determined according to GB/T1729-1979;
5. the drying time is determined according to GB/T1728-;
6. water resistance was determined as GB/T1733 + 1993;
7. alkali resistance was determined as in GB/T9265-2009;
8. the scrub resistance is determined according to GB/T9266-;
9. artificial aging resistance was determined according to GB/T1865-.
Secondly, testing the air purification performance:
the paint samples were sprayed on asbestos fibre cement boards of 160mm by 160mm in size, with a coating thickness of about 200 μm, and cured for 72h in an environment with a humidity of 50% and a temperature of 25 ℃. Respectively simulating the environments with the pollution concentrations of NOx, methyl mercaptan, toluene and formaldehyde of 400 mu g/L, 200 mu g/L and 200 mu g/L in a sealed light-proof climate box with the size of 500mm multiplied by 500mm, sampling the air in the climate box through a micro-sampling pump, and determining the gas content change in the degradation process by adopting a gas chromatography. Firstly, fixing a well-maintained sample to be tested on a sample table, placing a climate box in an indoor visible light environment to enable the sample to be tested to fully receive visible light, closing a climate box cover and sealing, connecting a bottom air pressure balancing port to a water tank so as to keep the air pressure and the concentration of polluted gas in the climate box during sampling, starting a convection fan, keeping the concentrations of the gases at all positions in the climate box equal, introducing the polluted gas to the initial concentration, then closing an air inlet, and starting a photodegradation process;
1. the removal rate of the contaminated gas is calculated according to the formula (1):
q=（C0 — Ct）V/(S×t） （1）
wherein q is the removal rate of the polluted gas of the sample, and is [ mu ] g/(m)2•s）；C0The initial concentration of contaminant gas, μ g/m, at the beginning of degradation3；CtIs the equilibrium concentration of the contaminated gas at time t, μ g/m3(ii) a V is the gas volume of the experimental box, m3(ii) a S is the surface area of the coating, m2(ii) a t is the time elapsed from the start of the test to the end of the degradation, s;
2. the removal rate of the contaminated gas is calculated according to the formula (2):
η=（C0 — Ct）/ C0×100% （2）
wherein eta is the removal rate of the polluted gas,%; c0The initial concentration of contaminant gas, μ g/m, at the beginning of degradation3；CtIs the equilibrium concentration of the contaminated gas at time t, μ g/m3(ii) a t is the time elapsed from the start of the test to the end of the degradation, s;
the results of the above tests are shown in tables 1 and 2 below:
TABLE 1
TABLE 2
Claims (8)
1. A coating with visible light catalysis function is characterized in that:
the specific formula of the coating comprises the following components in parts by weight:
40-60 parts of aqueous acrylic emulsion
3-8 parts of carbon-molybdenum modified titanium dioxide powder
1-2 parts of bismuth molybdate powder
2-5 parts of bismuth titanate powder
0.5-2 parts of thickening agent
1-2 parts of dispersant
0.1-1 part of flatting agent
0.1-1.2 parts of film-forming assistant
0.1 to 1.5 parts of wetting agent
0.1-0.4 part of defoaming agent
10-18 parts of filler
0.5-1.5 parts of water-based nano silicon dioxide
15-35 parts of deionized water;
adding triethanolamine and glycerol into an organic acid aqueous solution, then adding molybdate, stirring and dissolving to obtain a solution A, adding sodium fluosilicate into a titanyl sulfate aqueous solution, dissolving completely to obtain a solution B, then pouring the solution A into the solution B, stirring strongly for 30-60 minutes, transferring into a polytetrafluoroethylene hydrothermal reaction kettle, reacting for 10-16 hours at 180-250 ℃, cooling to room temperature, filtering the reaction solution, filtering the filtered powder, and washing and drying to obtain the carbon-molybdenum modified titanium dioxide powder;
dissolving bismuth sulfate and ammonium phosphomolybdate in deionized water, transferring the obtained solution into a polytetrafluoroethylene hydrothermal reaction kettle, reacting at 180-220 ℃ for 5-8 hours, cooling to room temperature, filtering the liquid after the reaction is finished, washing the filtrate with the deionized water for three times, and drying at 75-100 ℃ for 2-5 hours to obtain bismuth molybdate powder;
dissolving ammonium fluotitanate in a mixed solution of deionized water and an alcohol ether solvent, stirring and controlling the temperature, adding an acidified bismuth salt aqueous solution into the mixed solution, adding an alcohol hydrothermal auxiliary agent to obtain a reaction solution, adjusting the pH of the reaction solution to 8-10 with an alkali solution, transferring the reaction solution into a polytetrafluoroethylene hydrothermal reaction kettle, carrying out hydrothermal reaction, cooling to room temperature, carrying out centrifugal separation, washing with water and ethanol for multiple times, and carrying out vacuum drying to obtain bismuth titanate powder.
2. The coating with visible light catalytic function as claimed in claim 1, wherein:
the organic acid aqueous solution is one of 1,3, 5-benzene tricarboxylic acid aqueous solution, oxalic acid aqueous solution and phenyl hexacarboxylic acid aqueous solution;
in the organic acid aqueous solution, the mass concentration of the organic acid is 10-30 wt%;
the mass ratio of the organic acid aqueous solution to the triethanolamine to the glycerol is 50-80: 1-10: 2-13;
the molybdate is one of ammonium molybdate and potassium molybdate;
the addition amount of the molybdate is 20-35% of the mass of the organic acid.
3. The coating with visible light catalytic function as claimed in claim 1, wherein:
the mass ratio of the titanyl sulfate aqueous solution to the sodium fluosilicate is 100: 1-6;
the mass concentration of the titanyl sulfate in the titanyl sulfate aqueous solution is 20-45 wt%;
the mass ratio of the solution A to the solution B is 10: 5-8;
stirring with strong force at a stirring speed of 3000-5000 rpm;
and (3) washing and drying, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 70-95 ℃ for 10-14 hours.
4. The coating with visible light catalytic function as claimed in claim 1, wherein:
the mass ratio of the bismuth sulfate to the ammonium phosphomolybdate to the deionized water is 7-18: 10-33: 150-220.
5. The coating with visible light catalytic function as claimed in claim 1, wherein:
the alcohol ether solvent is one of diethylene glycol butyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether;
the bismuth salt aqueous solution is one of a bismuth sulfate aqueous solution, a bismuth nitrate aqueous solution and a bismuth chloride aqueous solution;
the preparation method of the acidified bismuth salt aqueous solution comprises the steps of adjusting the pH of a bismuth sulfate aqueous solution to 3-5 by using sulfuric acid, adjusting the pH of a bismuth nitrate aqueous solution to 3-5 by using nitric acid, or adjusting the pH of a bismuth chloride aqueous solution to 3-5 by using hydrochloric acid;
the mass concentration of bismuth salt in the bismuth salt aqueous solution is 8-20 wt%;
the alcohol hydrothermal auxiliary agent is one of glycerol, glycol and pentaerythritol.
6. The coating with visible light catalytic function as claimed in claim 1, wherein:
the alkali liquor is one of sodium hydroxide aqueous solution or ammonia water;
the mass ratio of the ammonium fluotitanate to the deionized water to the alcohol ether solvent to the acidified bismuth salt aqueous solution to the alcohol hydrothermal auxiliary agent is 7-18: 10-20: 8-15: 9-26: 3-7;
the stirring temperature is controlled, the stirring speed is 700-1200 rpm, and the temperature is 50-80 ℃;
the hydrothermal reaction is carried out at the temperature of 200-250 ℃ for 3-7 hours.
7. The coating with visible light catalytic function as claimed in claim 1, wherein:
the water-based acrylic emulsion is water-based lauryl alcohol acrylate copolymer emulsion;
the thickening agent is an ethoxy polyurethane water-soluble polymer;
the dispersant is methoxy polyethylene glycol ether sodium salt;
the leveling agent is aliphatic waterborne polyurethane;
the film-forming additive is dodecyl alcohol ester;
the wetting agent is polyether and dimethyl siloxane graft copolymer;
the defoaming agent is modified polydimethylsiloxane;
the filler is one of calcium carbonate and talcum powder, and the particle size is 800-1100 meshes.
8. The method for preparing a coating according to claim 1, characterized in that:
according to the specific formula of the coating in parts by weight, firstly, adding the water-based acrylic emulsion and deionized water into a mixing kettle, sequentially adding the dispersing agent, the flatting agent, the film forming aid, the wetting agent and the defoaming agent at a stirring speed of 2000-4000 rpm, increasing the stirring speed to 5000-6500 rpm, sequentially and slowly adding the carbon-molybdenum modified titanium dioxide powder, the bismuth molybdate powder, the bismuth titanate powder, the water-based nano silicon dioxide, the filler and the thickening agent, continuously stirring for 2-5 hours, and discharging to obtain a coating finished product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535911A (en) * | 2023-05-04 | 2023-08-04 | 浙江绿色德环保科技股份有限公司 | Visible light photocatalyst coating and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535911A (en) * | 2023-05-04 | 2023-08-04 | 浙江绿色德环保科技股份有限公司 | Visible light photocatalyst coating and preparation method thereof |
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