CN115746652A - Coating with air purification and self-cleaning functions, coating and preparation method thereof - Google Patents
Coating with air purification and self-cleaning functions, coating and preparation method thereof Download PDFInfo
- Publication number
- CN115746652A CN115746652A CN202211434595.2A CN202211434595A CN115746652A CN 115746652 A CN115746652 A CN 115746652A CN 202211434595 A CN202211434595 A CN 202211434595A CN 115746652 A CN115746652 A CN 115746652A
- Authority
- CN
- China
- Prior art keywords
- coating
- tio
- stirring
- drying
- solution
- 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.)
- Granted
Links
Images
Abstract
The invention relates to the field of coatings, and discloses a coating with air purification and self-cleaning functions, a coating and a preparation method thereof. Firstly, the paint of the invention simultaneously contains hydrophobic nano SiO 2 And hydrophilic black TiO 2 The hollow nanospheres can provide air purification and self-cleaning functions for the coating of the coating. Secondly, the present invention hydrophilic black TiO 2 The hollow nanospheres have the characteristics of high visible light response and slow photon-generated carrier recombination rate due to the fact that the hollow nanospheres have the trivalent titanium defect and the hollow nanosphere structure, and have stronger photocatalytic degradation capability on organic pollutants in air. In addition, the petroleum resin is introduced into the styrene-butadiene-styrene block copolymer, so that a crosslinking reaction can occur, and the viscosity of the bonding layer is increased.
Description
Technical Field
The invention relates to the field of coatings, in particular to a coating with air purification and self-cleaning functions, a coating and a preparation method thereof.
Background
The indoor air pollution such as formaldehyde, tobacco and the like seriously harms the health of people, and a simple, convenient and effective method is developed to treat the harm of the indoor air pollution, which is a problem urgently needed to be solved by the human society. Semiconductor photocatalysis has been recognized as an ideal way to treat indoor air pollution. Wherein, tiO 2 The composite material has the advantages of low price, no toxicity, universality and the like, and can be applied to the degradation of organic pollutants. However, pure TiO 2 There are two well-known disadvantages that prevent its large-scale application in photocatalysis. One is TiO 2 The ultraviolet light has activity only under the ultraviolet light, and the ultraviolet light accounts for less than 5 percent of the sunlight due to a wide band gap of 3.0 to 3.2 eV. The second is TiO 2 The high electron-hole recombination rate of (2) results in low quantum yield and low efficiency of the photocatalytic reaction. Therefore, there is an urgent need to prepare TiO with high visible light response and slow photon-generated carrier recombination rate 2 。
On the other hand, hydrophobic nano SiO is utilized 2 The prepared super-hydrophobic coating not only can prevent the metal from rusting and prevent the paper, the fabric, the wood and the like from absorbing water and mildewing, but also has a self-cleaning function. Therefore, if TiO with photocatalytic performance is to be used 2 And hydrophobic nano SiO 2 The composite coating is sprayed on the surface of a matrix to form a functional coating, so that the household article can be endowed with the functions of removing indoor air pollution and self-cleaning. In the prior art, there are reports of TiO 2 Or SiO 2 Mixing with styrene-butadiene-styrene block copolymer (SBS) to prepare the coating. However, the viscosity of the coating is not ideal enough, so that the coating has poor adhesion with the surface of a substrate, has poor coating stability and is easy to fall off.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cleaning agent with air purification and self-cleaning functionsThe coating and the preparation method thereof. Firstly, the coating of the invention simultaneously contains hydrophobic nano SiO 2 And hydrophilic black TiO 2 The hollow nanospheres can provide air purification and self-cleaning functions for the coating of the coating. Secondly, the hydrophilic black TiO of the invention 2 The hollow nanospheres have the characteristics of high visible light response and slow photon-generated carrier recombination rate due to the fact that the hollow nanospheres have trivalent titanium defects and hollow nanosphere structures, and have stronger photocatalytic degradation capability on organic air pollutants. In addition, when the petroleum resin is introduced into SBS, cross-linking reaction can occur, and viscosity of the adhesive layer is increased.
The specific technical scheme of the invention is as follows:
in a first aspect, the invention provides a coating with air purification and self-cleaning functions, which comprises the following components in parts by weight:
bonding layer composition: 3 to 8 parts of styrene-butadiene-styrene block copolymer (SBS), 2 to 10 parts of petroleum resin and 80 to 120 parts of ethyl acetate.
Functional layer composition: hydrophobic nano SiO 2 3 to 5 parts of hydrophilic black TiO 2 Hollow nanosphere1 to 5 parts of ethanol and 80 to 120 parts of ethanol.
The defects that titanium dioxide only has activity under ultraviolet light and has low visible light response, and the quantum yield and the low efficiency of photocatalytic reaction are caused by high electron-hole recombination rate are overcome. The invention prepares hydrophilic black TiO with high visible light response and slow photon-generated carrier recombination rate 2 A hollow nanosphere. Specifically, the hydrophilic black TiO of the present invention 2 The hollow nanospheres are made of TiO under high temperature 2 The tetravalent titanium in the titanium dioxide is reduced into trivalent titanium by sodium borohydride and ethylenediamine, so that a trivalent titanium defect is formed, a new impurity energy level is generated, the energy band gap is further shortened, the photon-generated carrier rate is improved, and therefore visible light absorption is promoted, and meanwhile, tiO 2 The color changes from white to black. More importantly, black TiO with trivalent titanium defects 2 Has a large number of oxygen vacancies, and can promote the photoresponse in the near infrared region. Thus, the hydrophilic black TiO of the present invention 2 The trivalent titanium defect in the hollow nanosphere becomes an active site for chemical reaction, thereby being largeGreatly improves the reaction efficiency of photocatalytic degradation of organic pollutants. Further, the hydrophilic black TiO of the present invention 2 Hollow nanosphere and common black TiO with trivalent titanium defect 2 In contrast, it also appears as a hollow sphere structure. On one hand, the mesoporous and high specific surface area of the hollow sphere are utilized, so that the polluted air can be efficiently adsorbed in a physical mode; on the other hand, the diffusion distance of the photoproduction electron-hole pair can be reduced through refraction and scattering of light in the hollow inner cavity, so that sunlight can be more fully utilized, and the efficiency of photocatalytic degradation of polluted air is further improved.
For containing SiO 2 And TiO 2 The invention discloses a styrene-butadiene-styrene block copolymer coating with low viscosity and poor adhesion with the surface of a matrix, and creatively provides a spraying method of a bonding layer and a functional layer, wherein the coating is designed into two components of the bonding layer and the functional layer: in the bonding layer, petroleum resin and SBS are compounded and then can generate a crosslinking reaction to form a dense space crosslinking structure, so that the viscosity of the bonding layer solution can be improved. In the functional layer, hydrophilic black TiO is prepared by using the characteristics of high volatility of ethanol capable of dissolving polar and nonpolar materials 2 Hollow nanospheres and hydrophobic nano SiO 2 Mixed and dispersed in ethanol to serve as functional layer solution, thereby endowing the coating with air purification and self-cleaning functions.
Preferably, 3.5 parts of styrene-butadiene-styrene block copolymer (SBS), 6.5 parts of petroleum resin, 100 parts of ethyl acetate and hydrophobic nano SiO 2 3 parts of hydrophilic black TiO 2 Hollow nanosphere2 parts of ethanol and 100 parts of ethanol.
Preferably, the petroleum resin is selected from the group consisting of C5 petroleum resins, C9 petroleum resins; the hydrophobic nano SiO 2 The particle size of (A) is 20 to 100nm; the hydrophilic black TiO 2 The particle size of the hollow nanospheres is 110-150nm.
Preferably, the hydrophilic black TiO 2 The preparation method of the hollow nanospheres comprises the following steps:
(a) Adding tetraethoxysilane dropwise into a mixed solution of water, absolute ethyl alcohol and ammonia water, stirring, centrifuging and washingWashing and drying to obtain SiO 2 And (3) granules.
(b) Mixing SiO 2 Ultrasonically dispersing the particles in absolute ethyl alcohol to obtain a solution A; dissolving tetrabutyl titanate (TBOT) in absolute ethyl alcohol to obtain a solution B; adding the solution B and ammonia water into the solution A, heating and stirring for reaction, centrifuging, washing, drying and calcining to obtain SiO 2 @TiO 2 Nanospheres.
(c) Mixing SiO 2 @TiO 2 Adding the nanospheres into alkali liquor, heating and stirring for reaction, centrifuging, washing and drying to obtain TiO 2 The hollow nanospheres.
(d) Mixing TiO with 2 Adding the hollow nanospheres and sodium borohydride into ethylenediamine, performing ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, performing solvothermal reaction at 160 to 200 ℃ for 45 to 50h, centrifuging, washing and drying to obtain hydrophilic black TiO 2 A hollow nanosphere.
Design of different shapes of black TiO 2 The structure is an effective method for improving the photocatalytic efficiency. The invention adopts a solvothermal method, uses ethylenediamine as a solvent and a reducing agent, uses sodium borohydride as an auxiliary reducing agent, and reduces white TiO with a hollow structure at high temperature and high pressure 2 Preparing hydrophilic black TiO from hollow nano-spheres 2 A hollow nanosphere. The mesoporous and high specific surface area of the hollow sphere are utilized to efficiently adsorb the polluted air, meanwhile, the diffusion distance of a photoproduction electron-hole pair is reduced through refraction and scattering of light in the hollow inner cavity, and sunlight is fully utilized, so that the polluted air is efficiently degraded through photocatalysis.
Preferably, in the step (a), the volume ratio of the water, the absolute ethyl alcohol, the ammonia water (with the concentration of 25 to 28wt%) and the tetraethoxysilane is (10 to 15): (60 to 80): (1 to 3): (1.5 to 4). Further preferably 12.9:69:1.86:2.58.
preferably, in step (b), the SiO 2 The dosage ratio of the particles to the absolute ethyl alcohol is (0.2 to 0.5) g:100ml; further preferably 0.3g:100ml.
Preferably, in the step (b), the volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is (1.5 to 3): 100, respectively; more preferably 2:100.
preferably, in the step (b), the ammonia water (with the concentration of 25 to 28wt%) is used in an amount of 0.5 to 1 percent of the volume of the absolute ethyl alcohol; further preferably 0.75%.
Preferably, in the step (b), the temperature for heating and stirring the reaction is 55 to 65 ℃;
preferably, in the step (b), the calcining temperature is 700 to 1000 ℃, and the calcining time is 0.5 to 1.5 hours; more preferably, the calcination temperature is 800 ℃ and the calcination time is 1 hour.
Preferably, in step (c), the alkali liquor is NaOH solution with the concentration of 0.8-1.2mol/L, and the SiO is 2 @TiO 2 The dosage ratio of the nanospheres to the NaOH solution is 1g (50-80) ml; the temperature for heating and stirring the reaction is 75 to 85 ℃.
Preferably, in step (d), the TiO is 2 The dosage ratio of the hollow nanospheres to the sodium borohydride and the ethylenediamine is (1 to 3) g: (1 to 3) g: (50-80) ml; more preferably 1g:1g:60ml.
Preferably, in the steps (a) - (d), the washing is water washing and ethanol washing; the drying temperature is 55 to 65 ℃, and the drying time is 10 to 15h.
In a second aspect, the present invention provides a method for preparing a coating layer with air purification and self-cleaning functions from the above coating, comprising the following steps:
(1) Preparation of the bonding layer: dissolving styrene-butadiene-styrene block copolymer and petroleum resin in ethyl acetate, and uniformly stirring to obtain a bonding layer solution; and uniformly spraying the bonding layer solution on the surface of the substrate, and drying to form the bonding layer.
(2) Preparation of the functional layer: hydrophobic nano SiO 2 And hydrophilic black TiO 2 Adding the hollow nanospheres into ethanol, stirring, and performing ultrasonic oscillation to obtain functional layer dispersion liquid; and uniformly spraying the functional layer dispersion liquid on the surface of the bonding layer, and drying to form the functional layer.
Preferably, in the step (1), the rotation speed of the stirring is 1200 to 1500rpm, and the stirring time is 20 to 36h.
Preferably, in the step (2), the rotation speed of the stirring is 700 to 1000rpm, the stirring time is 10 to 20min, the ultrasonic oscillation time is 20 to 50min, and the temperature is room temperature.
Preferably, in the step (1) and the step (2), the spraying pressure is 0.2 to 0.5MPa, the spraying distance to the substrate is 10 to 20cm, the drying temperature is room temperature, and the drying time is 10 to 20min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention utilizes a solvothermal method, uses ethylenediamine as a solvent and a reducing agent, uses sodium borohydride as an auxiliary reducing agent, and reduces white TiO with a hollow structure at high temperature and high pressure 2 Preparing hydrophilic black TiO from hollow nano-spheres 2 A hollow nanosphere. The hydrophilic black TiO 2 The hollow nanospheres have trivalent titanium defects and oxygen vacancies, can generate new impurity energy levels, further shorten the energy band gap and promote the visible light absorption performance. The mesoporous and high specific surface area of the hollow sphere are utilized to efficiently adsorb the polluted air, meanwhile, the diffusion distance of a photoproduction electron-hole pair is reduced through refraction and scattering of light in the hollow inner cavity, and sunlight is fully utilized, so that the polluted air is efficiently degraded through photocatalysis.
(2) The invention creatively provides a spraying method of a bonding layer and a functional layer, which compounds petroleum resin and SBS to generate a crosslinking reaction, form a dense space crosslinking structure, improve the viscosity of a bonding layer solution and the like. Meanwhile, the hydrophilic black TiO is prepared by using the characteristics of high volatility of ethanol which can dissolve polar and nonpolar materials 2 Hollow nanosphere and hydrophobic nano SiO 2 Mixed and dispersed in ethanol as functional layer solution, thereby endowing the coating with air purification and self-cleaning functions.
Drawings
FIG. 1 shows TiO prepared in example 1 2 Hollow nanospheres (a) and hydrophilic black TiO 2 Photo of hollow nanospheres (b);
FIG. 2 shows the hydrophilic black TiO prepared in example 1 2 SEM picture of the nanometer hollow sphere;
FIG. 3 shows the hydrophilic black TiO prepared in example 1 2 XRD pattern of the hollow nanospheres;
FIG. 4 is a graph of the change in water contact angle after 60 rubs of the coating prepared in example 1;
FIG. 5 is an SEM image of the surfaces of the bonding layer (a) and the functional layer (b) of the coating prepared in example 1;
FIG. 6 is a picture of the self-cleaning properties of the coating prepared in example 1;
FIG. 7 is a graph of the water contact angle of the coating prepared in example 1 on stainless steel (a), fabric (b), glass sheet (c), A4 paper (d);
FIG. 8 is test data of photocatalytic degradation of formaldehyde gas for the coating prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A coating with air purification and self-cleaning functions comprises the following components in parts by weight:
bonding layer composition: 3 to 8 parts (preferably 3.5 parts) of styrene-butadiene-styrene block copolymer (SBS), 2 to 10 parts (preferably 6.5 parts) of petroleum resin and 80 to 120 parts (preferably 100 parts) of ethyl acetate.
Functional layer components: hydrophobic nano SiO 2 3 to 5 parts (preferably 3 parts) of hydrophilic black TiO 2 Hollow nanosphere1 to 5 parts (preferably 2 parts) of ethanol and 80 to 120 parts (preferably 100 parts) of ethanol.
Preferably, the petroleum resin is selected from the group consisting of C5 petroleum resins, C9 petroleum resins; the hydrophobic nano SiO 2 The particle size of (A) is 20 to 100nm; the hydrophilic black TiO 2 The particle size of the hollow nanospheres is 110 to 150nm.
Preferably, the hydrophilic black TiO 2 The preparation method of the hollow nanospheres comprises the following steps:
(a) Adding tetraethoxysilane into a mixed solution of water, absolute ethyl alcohol and ammonia water dropwise, stirring, centrifuging, washing (water washing and ethanol washing), and drying (55 to 65 ℃ and 10 to 15h) to obtain SiO 2 And (3) particles. The volume ratio of the water to the absolute ethyl alcohol to the ammonia water (the concentration is 25 to 28wt%) to the tetraethoxysilane is (10 to 15): (60 to 80): (1 to 3): (1.5 to 4)(ii) a Further preferably 12.9.
(b) Mixing SiO 2 Ultrasonically dispersing the particles in absolute ethyl alcohol to obtain a solution A; dissolving tetrabutyl titanate (TBOT) in absolute ethyl alcohol to obtain a solution B; adding the solution B and ammonia water into the solution A, heating and stirring at 55-65 ℃ for reaction, centrifuging, washing (washing with water and washing with ethanol), drying (55-65 ℃, 10-15h), calcining (700-1000 ℃, 0.5-1.5h, more preferably 800 ℃,1 h) to obtain SiO 2 @TiO 2 Nanospheres. The SiO 2 The dosage ratio of the granules to the absolute ethyl alcohol is (0.2 to 0.5) g:100ml; further preferably 0.3g:100ml. The volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is (1.5 to 3): 100; more preferably 2:100. the amount of the ammonia water (the concentration is 25 to 28wt%) is 0.5 to 1 percent of the volume of the absolute ethyl alcohol; further preferably 0.75%.
(c) Mixing SiO 2 @TiO 2 Adding nanosphere to alkaline solution (preferably 0.8-1.2mol/L NaOH solution, siO) 2 @TiO 2 The volume ratio of the nanospheres to the NaOH solution is 1g (50-80) ml), the nanospheres and the NaOH solution are heated and stirred at 75-85 ℃ for reaction, and the reaction product is centrifuged, washed (water and ethanol), dried (55-65 ℃ and 10-15h) to obtain TiO 2 The hollow nanospheres.
(d) Adding TiO into the mixture 2 Adding the hollow nanospheres and sodium borohydride into ethylenediamine, ultrasonically dispersing, moving into a high-pressure reaction kettle, carrying out thermal reaction on a solvent at 160-200 ℃ for 45-50h, centrifuging, washing (washing with water and ethanol), and drying (55-65 ℃ and 10-15h) to obtain the hydrophilic black TiO 2 The hollow nanospheres. The TiO is 2 The dosage ratio of the hollow nanospheres to the sodium borohydride and the ethylenediamine is (1 to 3) g: (1 to 3) g: (50 to 80) ml; more preferably 1g:1g:60ml.
A method for preparing a coating with air purification and self-cleaning functions by using the coating comprises the following steps:
(1) Preparation of the bonding layer: dissolving a styrene-butadiene-styrene block copolymer and petroleum resin in ethyl acetate, and uniformly stirring (1200-1500 rpm, 20-36h) to obtain a bonding layer solution; and uniformly spraying the bonding layer solution on the surface of the substrate (the spraying pressure is 0.2-0.5 MPa, and the spraying distance is 10-20cm), and drying at room temperature for 10-20min to form the bonding layer.
(2) Preparation of the functional layer: hydrophobic nano SiO 2 And hydrophilic black TiO 2 Adding the hollow nanospheres into ethanol, stirring (700 to 1000rpm,10 to 20min), and ultrasonically oscillating at room temperature (20 to 50min) to obtain a functional layer dispersion liquid; and uniformly spraying the functional layer dispersion liquid on the surface of the bonding layer (the spraying pressure is 0.2 to 0.5MPa, and the spraying distance is 10 to 20cm), and drying at room temperature for 10 to 20min to form the functional layer.
Example 1
(1) 2.58 mL of ethyl orthosilicate was added dropwise to a mixed solution of 12.9 mL of water, 69 mL of anhydrous ethanol and 1.86 mL of aqueous ammonia (concentration of 28% by weight). Then stirring for 6h at room temperature (600 rpm/25 ℃), centrifuging, washing with deionized water and ethanol, and drying for 12h at 60 ℃ to obtain SiO 2 And (3) granules.
(2) 0.3g of dried SiO 2 The particles were ultrasonically dispersed in 100mL of absolute ethanol to give solution a. 2mL of tetrabutyltitanate (TBOT) was dissolved in 100mL of absolute ethanol to obtain a solution B. Adding solution B and 0.75mL ammonia water (28 wt%) into solution A, stirring at 60 deg.C for 3h, centrifuging, washing with deionized water and ethanol, drying at 60 deg.C for 12h, and calcining at 800 deg.C for 1h to obtain SiO 2 @TiO 2 Nanospheres.
(3) 2g of SiO 2 @TiO 2 Adding the nanospheres into 120ml 1moL/L NaOH solution, heating and stirring at 80 ℃ for 4h, washing with deionized water and ethanol, and drying at 60 ℃ for 12h to obtain TiO 2 The hollow nanospheres.
(4) 1g of TiO 2 Putting the hollow nanospheres and 1g of sodium borohydride into a beaker, adding 60mL of ethylenediamine, ultrasonically dispersing, transferring into a high-pressure reaction kettle, and carrying out solvothermal reaction at 180 ℃ for 48 hours. Fully washing with absolute ethyl alcohol and deionized water, and drying at 60 ℃ for 12h to obtain hydrophilic black TiO 2 The hollow nanospheres.
(5) 3.5g SBS and 100ml ethyl acetate solution were added into a beaker and mixed, stirred magnetically for 30min at room temperature, added with 6.5g C9 petroleum resin and reacted at 1200rpm for 12h to obtain a homogeneous dispersion. Pouring the solution into a high-pressure spray can, and uniformly spraying the solution on the surface of the substrate by using high pressure (0.35 MPa), wherein the distance between the spout of the spray can and the substrate is 20cm. And after spraying, standing for 1min until the coating is cured.
(6) Taking 3g of hydrophobic nano SiO 2 (20 nm) and 2g of hydrophilic black TiO 2 The hollow nanospheres (130 nm) were dissolved in a beaker of 100ml ethanol and magnetically stirred at 700rpm for 10min. Stopping stirring, and placing in an ultrasonic machine at room temperature to vibrate for 30min to obtain uniform dispersion liquid. Pouring the liquid into a high-pressure spraying pot, and uniformly spraying the liquid on the surface of the substrate by using high pressure (0.35 MPa), wherein the distance between the pot mouth of the spraying pot and the substrate is 20cm. After spraying, standing for 10min, and completely drying the coating to obtain the coating with indoor air pollution removing and self-cleaning functions.
Example 2
(1) 4 mL of ethyl orthosilicate was added dropwise to a mixed solution of 15 mL of water, 80mL of anhydrous ethanol, and 3mL of aqueous ammonia (concentration of 28% by weight). Then stirring for 6h at room temperature (600 rpm/25 ℃), centrifuging, washing with deionized water and ethanol, and drying for 12h at 60 ℃ to obtain SiO 2 And (3) granules.
(2) 0.5g of dried SiO 2 The particles were ultrasonically dispersed in 100mL of absolute ethanol to give solution a. 3mL of tetrabutyltitanate (TBOT) was dissolved in 100mL of anhydrous ethanol to obtain a solution B. Adding the solution B and 1mL ammonia water (with concentration of 28 wt%) into the solution A, stirring at 60 deg.C for 3h, centrifuging, washing with deionized water and ethanol, drying at 60 deg.C for 12h, and calcining at 1000 deg.C for 1h to obtain SiO 2 @TiO 2 Nanospheres.
(3) 6g of SiO 2 @TiO 2 Adding nanosphere into 320ml 1.2mol/L NaOH solution, heating and stirring at 85 deg.C for 4 hr, washing with deionized water and ethanol, and drying at 60 deg.C for 12 hr to obtain TiO 2 The hollow nanospheres.
(4) 3g of TiO 2 And (3) putting the hollow nanospheres and 3g of sodium borohydride into a beaker, adding 80mL of ethylenediamine, performing ultrasonic dispersion, transferring the mixture into a high-pressure reaction kettle, and performing solvothermal reaction for 48 hours at 180 ℃. Fully washing with absolute ethyl alcohol and deionized water, and drying at 55 ℃ for 15h to obtain hydrophilic black TiO 2 The hollow nanospheres.
(5) 3g SBS and 100ml ethyl acetate solution were added to a beaker and mixed, magnetically stirred at room temperature for 30min, added with 10g C5 petroleum resin, reacted at 1200rpm for 12h to obtain a uniform dispersion. Pouring the solution into a high-pressure spray can, and uniformly spraying the solution on the surface of the substrate by using high pressure (0.5 MPa), wherein the distance between the spout of the spray can and the substrate is 20cm. And after spraying, standing for 1min until the coating is cured.
(6) 5g of hydrophobic nano SiO 2 (100 nm) and 1g hydrophilic Black TiO 2 The hollow nanospheres (150 nm) were dissolved in a beaker of 100ml ethanol and magnetically stirred at 700rpm for 10min. Stopping stirring, and placing in an ultrasonic machine at room temperature to vibrate for 30min to obtain uniform dispersion liquid. Pouring the liquid into a high-pressure spraying pot, and uniformly spraying the liquid on the surface of the substrate by using high pressure (0.5 MPa), wherein the distance between the pot mouth of the spraying pot and the substrate is 20cm. After spraying, standing for 10min, and completely drying the coating to obtain the coating with the functions of removing indoor air pollution and self-cleaning.
Example 3
(1) 1.5mL of ethyl orthosilicate was added dropwise to a mixed solution of 10 mL of water, 60mL of anhydrous ethanol, and 1.5mL of aqueous ammonia (concentration of 28% by weight). Then stirring for 6h at room temperature (600 rpm/25 ℃), centrifuging, washing with deionized water and ethanol, and drying for 12h at 60 ℃ to obtain SiO 2 And (3) granules.
(2) 0.5g of dried SiO 2 The particles were ultrasonically dispersed in 100mL of absolute ethanol to give solution a. 1.5mL of tetrabutyltitanate (TBOT) was dissolved in 100mL of anhydrous ethanol to obtain solution B. Adding solution B and 0.5mL ammonia water (28 wy%) into solution A, stirring at 60 deg.C for 3h, centrifuging, washing with deionized water and ethanol, drying at 65 deg.C for 10h, and calcining at 800 deg.C for 1h to obtain SiO 2 @TiO 2 Nanospheres.
(3) 2g of SiO 2 @TiO 2 Adding the nanospheres into 120ml of 0.8mol/L NaOH solution, heating and stirring at 75 ℃ for 4h, washing with deionized water and ethanol, and drying at 60 ℃ for 12h to obtain TiO 2 The hollow nanospheres.
(4) 1g of TiO 2 Adding the hollow nanospheres and 1g of sodium borohydride into a beaker, adding 50mL of ethylenediamine, ultrasonically dispersing, and transferring to a high-pressure reaction kettleAnd carrying out solvothermal reaction for 48h at 180 ℃. Fully washing with absolute ethyl alcohol and deionized water, and drying at 60 ℃ for 12h to obtain hydrophilic black TiO 2 The hollow nanospheres.
(5) Adding 8g of SBS and 100ml of ethyl acetate solution into a beaker, mixing, magnetically stirring for 30min at room temperature, adding 3g of C9 petroleum resin, and reacting for 12h at the rotating speed of 1200rpm to obtain uniform dispersion. Pouring the liquid into a high-pressure spraying pot, uniformly spraying the liquid on the surface of the substrate by using high pressure (0.2 MPa) and spraying out, wherein the distance between the pot mouth of the spraying pot and the substrate is 10cm. And after spraying, standing for 1min until the coating is cured.
(6) Taking 4g of hydrophobic nano SiO 2 (60 nm) and 2g of hydrophilic black TiO 2 The hollow nanospheres (110 nm) were dissolved in a beaker of 100ml ethanol and magnetically stirred at 700rpm for 10min. Stopping stirring, and placing in an ultrasonic machine at room temperature to vibrate for 30min to obtain uniform dispersion liquid. Pouring the liquid into a high-pressure spraying pot, and uniformly spraying the liquid on the surface of the substrate by using high pressure (0.2 MPa), wherein the distance between the pot mouth of the spraying pot and the substrate is 10cm. After spraying, standing for 10min, and completely drying the coating to obtain the coating with the functions of removing indoor air pollution and self-cleaning.
Performance testing
FIG. 1 shows TiO prepared in example 1 2 Hollow nanospheres (a) and hydrophilic black TiO 2 Photo of hollow nanospheres (b).
FIG. 2 shows hydrophilic black TiO of example 1 2 SEM image of the hollow nanospheres; as can be seen, the hydrophilic black TiO 2 The hollow nanospheres are relatively regular round, some particles are not completely coated, a hollow structure can be seen, and the particle size is about 130nm.
FIG. 3 shows the hydrophilic black TiO prepared in example 1 2 XRD pattern of the hollow nanospheres; as shown, the 2 θ angular positions correspond to Ti at 18.1 °,25.2 ° and 48.1 °, respectively 3 O 5 Is/are as follows(200) Crystal planes (JCPDF 23-0606) of (110) and (020) without rutile TiO 2 Has an amorphous diffraction peak, which indicates that the prepared hydrophilic black TiO 2 The existence of Ti in the hollow nanospheres 3+ 。
FIG. 4 is a graph of the change in water contact angle after 60 rubs of the coating prepared in example 1. First, a 100g weight was placed on the glass sample, and then the sample was pushed evenly onto 800 mesh sandpaper. Each wear movement is 10cm. After each 10 abrasions, the contact angle of the sample was measured. The wettability of the coating with the bonding layer of the SBS and C9 petroleum resin mixture is not obviously changed after 60 times of abrasion, the contact angle is 149.8 degrees, and the coating has excellent abrasion resistance.
Fig. 5 is an SEM image of the surface of the adhesive layer and the functional layer prepared in example 1, wherein (a) is the adhesive layer and (b) is the functional layer. Irregular micro-scale protrusions can be seen to cover the surface when the bonding layer is sprayed, the water contact angle is 81.7 degrees, and the hydrophilic state is still kept. After the functional layer is sprayed, the surface of the coating is in a multi-scale coarse structure, has the mastoid morphology similar to the lotus leaf surface, is a non-uniform aggregate formed by agglomeration of nano particles, and shows a super-hydrophobic state when the static contact angle of the coating is tested to be 155.6 degrees.
Fig. 6 is a picture of the self-cleaning performance of the coating prepared in example 1, sand is placed on the surface of the glass slide coated with the functional coating, water drops are dropped from the upper end of the glass, the sand rolls along with water drops, and the surface of the coating becomes very clean. This is because the low adhesion of the superhydrophobic coating to water droplets makes the water droplets tend to roll on the surface and difficult to stay; on the other hand, the affinity between the sandy soil and the water drops is greater than that between the sandy soil and the film, so that the sandy soil on the surface can be taken away when the water drops roll off from the surface of the super-hydrophobic coating. The coating prepared by the method has a good self-cleaning effect and can be widely applied in actual life.
FIG. 7 is a graph of the water contact angle of the coating prepared in example 1 on stainless steel (a), fabric (b), glass sheet (c), A4 paper (d); the water contact angles of the coatings on the surfaces of stainless steel, fabrics, glass sheets and A4 paper are measured and are all more than 150 degrees by using 8 mu L of water drops which fall on the surfaces of the coatings by means of self gravity, and the prepared coatings can be applied to various substrates, namely soft substrates and hard substrates, and can obtain good super-hydrophobic performance.
FIG. 8 is test data for formaldehyde degradation for coatings prepared in example 1; such asAs shown in the figure, the initial concentration of formaldehyde is 0.6mg/m 3 In the blank experiment without coating, the formaldehyde concentration is unchanged after 3h of illumination. When the coating prepared in example 1 was used as a catalyst, the formaldehyde concentration started to decrease after the irradiation with light. The formaldehyde concentration decreased slowly during the first 20 minutes, since the coating adsorbed a portion of the formaldehyde gas molecules before the experiment began and degraded the gas molecules occupying the surface active sites after the start of the light exposure. Thereafter, the formaldehyde concentration dropped rapidly, due to the catalyst being fully activated, hydrophilic black TiO 2 The trivalent titanium defect of the hollow nanospheres becomes an active site of chemical reaction, new impurity energy level can be generated, and the energy band gap is further shortened, so that the absorption of visible light is promoted. Hydrophilic black TiO with trivalent titanium defects 2 The hollow nanospheres have a large number of oxygen vacancies, increase the photoresponse of a near infrared region, improve the utilization rate of light and greatly promote the degradation of formaldehyde. The formaldehyde degradation rate reaches 99.1 percent in 120 min.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A coating with air purification and self-cleaning functions is characterized in that: the paint comprises the following components in parts by weight:
bonding layer composition: 3-8 parts of styrene-butadiene-styrene block copolymer, 2-10 parts of petroleum resin and 80-120 parts of ethyl acetate;
functional layer composition: hydrophobic nano SiO 2 3 to 5 parts of hydrophilic black TiO 2 1 to 5 parts of hollow nanospheres and 80 to 120 parts of ethanol.
2. The coating of claim 1, wherein:
the petroleum resin is selected from C5 petroleum resin and C9 petroleum resin;
the hydrophobic nano SiO 2 The particle size of (A) is 20 to 100nm;
the hydrophilic black TiO 2 The particle size of the hollow nanospheres is 110 to 150nm.
3. The coating of claim 1 or 2, wherein: the hydrophilic black TiO 2 The preparation method of the hollow nanospheres comprises the following steps:
(a) Adding tetraethoxysilane into a mixed solution of water, absolute ethyl alcohol and ammonia water dropwise, stirring, centrifuging, washing and drying to obtain SiO 2 Particles;
(b) Mixing SiO 2 Ultrasonically dispersing the particles in absolute ethyl alcohol to obtain a solution A; dissolving tetrabutyl titanate in absolute ethyl alcohol to obtain a solution B; adding the solution B and ammonia water into the solution A, heating and stirring for reaction, centrifuging, washing, drying and calcining to obtain SiO 2 @TiO 2 Nanospheres;
(c) Mixing SiO 2 @TiO 2 Adding the nanospheres into alkali liquor, heating and stirring for reaction, centrifuging, washing and drying to obtain TiO 2 A hollow nanosphere;
(d) Adding TiO into the mixture 2 Adding the hollow nanospheres and sodium borohydride into ethylenediamine, ultrasonically dispersing, moving into a high-pressure reaction kettle, carrying out solvent thermal reaction at 160-200 ℃ for 45-50h, centrifuging, washing and drying to obtain hydrophilic black TiO 2 The hollow nanospheres.
4. The coating of claim 3, wherein: in the step (a), the volume ratio of the water to the absolute ethyl alcohol to the ammonia water to the tetraethoxysilane is (10 to 15): (60 to 80): (1 to 3): (1.5 to 4); the concentration of the ammonia water is 25 to 28wt%.
5. The coating of claim 3, wherein: in the step (b), the step (c),
the SiO 2 The dosage ratio of the particles to the absolute ethyl alcohol is (A)0.2~0.5）g：100ml；
The volume ratio of the tetrabutyl titanate to the absolute ethyl alcohol is (1.5 to 3): 100;
the dosage of the ammonia water is 0.5 to 1 percent of the volume of the absolute ethyl alcohol; the concentration of the ammonia water is 25 to 28wt%;
the temperature for heating, stirring and reacting is 55 to 65 ℃;
the calcination temperature is 700 to 1000 ℃, and the calcination time is 0.5 to 1.5h.
6. The coating of claim 3, wherein: in the step (c),
the alkali liquor is NaOH solution with the concentration of 0.8-1.2mol/L, and the SiO 2 @TiO 2 The dosage ratio of the nanosphere to the NaOH solution is 1g (50 to 80) ml;
the temperature for heating and stirring the reaction is 75 to 85 ℃.
7. The coating of claim 3, wherein: in step (d), the TiO 2 The dosage ratio of the hollow nanospheres to sodium borohydride and ethylenediamine is (1 to 3) g: (1 to 3) g: (50 to 80) ml.
8. The coating of claim 4, wherein: in the steps (a) to (d), the washing is water washing and ethanol washing; the drying temperature is 55 to 65 ℃, and the drying time is 10 to 15h.
9. A method for preparing a coating layer having air cleaning and self-cleaning functions by using the coating material as claimed in any one of claims 1 to 8, characterized by comprising the steps of:
(1) Preparation of the bonding layer: dissolving styrene-butadiene-styrene block copolymer and petroleum resin in ethyl acetate, and uniformly stirring to obtain bonding layer solution; uniformly spraying the bonding layer solution on the surface of the substrate, and drying to form a bonding layer;
(2) Preparation of the functional layer: hydrophobic nano SiO 2 And hydrophilic black TiO 2 Adding the hollow nanospheres into ethanol, stirring, and ultrasonically oscillating to obtain functional layerDispersing; and uniformly spraying the functional layer dispersion liquid on the surface of the bonding layer, and drying to form the functional layer.
10. The method of claim 9, wherein:
in the step (1), the stirring speed is 1200-1500 rpm, and the stirring time is 20-36h;
in the step (2), the stirring speed is 700-1000rpm, the stirring time is 10-20min, the ultrasonic oscillation time is 20-50min, and the temperature is room temperature;
in the step (1) and the step (2), the spraying pressure is 0.2 to 0.5MPa, the spraying distance between the spraying pressure and the substrate is 10 to 20cm, the drying temperature is room temperature, and the drying time is 10 to 20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211434595.2A CN115746652B (en) | 2022-11-16 | 2022-11-16 | Paint and coating with air purification and self-cleaning functions and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211434595.2A CN115746652B (en) | 2022-11-16 | 2022-11-16 | Paint and coating with air purification and self-cleaning functions and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115746652A true CN115746652A (en) | 2023-03-07 |
| CN115746652B CN115746652B (en) | 2023-07-28 |
Family
ID=85372826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211434595.2A Active CN115746652B (en) | 2022-11-16 | 2022-11-16 | Paint and coating with air purification and self-cleaning functions and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115746652B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004035746A (en) * | 2002-07-04 | 2004-02-05 | Asahi Rubber Kk | Joint sealing material |
| CN103880066A (en) * | 2014-02-19 | 2014-06-25 | 陕西科技大学 | Preparation method of cubic phase BaTiO3 hollow nanospheres |
| CN105985698A (en) * | 2015-02-09 | 2016-10-05 | 章道义 | Insulated waterproof paint and preparation method thereof |
| CN107998438A (en) * | 2017-12-18 | 2018-05-08 | 广东泰宝医疗科技股份有限公司 | A kind of sustained anti-microbial bearing hydrocolloid dressing and preparation method thereof |
| CN109833862A (en) * | 2019-01-22 | 2019-06-04 | 太原理工大学 | A kind of preparation method of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material |
| CN111821966A (en) * | 2019-04-22 | 2020-10-27 | 新疆大学 | Black TiO2Preparation method of nanosheet photocatalyst |
| CN112915989A (en) * | 2021-01-27 | 2021-06-08 | 中国建筑材料科学研究总院有限公司 | SiO (silicon dioxide)2@TiO2Nano composite material and preparation method and application thereof |
-
2022
- 2022-11-16 CN CN202211434595.2A patent/CN115746652B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004035746A (en) * | 2002-07-04 | 2004-02-05 | Asahi Rubber Kk | Joint sealing material |
| CN103880066A (en) * | 2014-02-19 | 2014-06-25 | 陕西科技大学 | Preparation method of cubic phase BaTiO3 hollow nanospheres |
| CN105985698A (en) * | 2015-02-09 | 2016-10-05 | 章道义 | Insulated waterproof paint and preparation method thereof |
| CN107998438A (en) * | 2017-12-18 | 2018-05-08 | 广东泰宝医疗科技股份有限公司 | A kind of sustained anti-microbial bearing hydrocolloid dressing and preparation method thereof |
| CN109833862A (en) * | 2019-01-22 | 2019-06-04 | 太原理工大学 | A kind of preparation method of redox graphene/titanium dioxide double shells hollow sphere composite photocatalyst material |
| CN111821966A (en) * | 2019-04-22 | 2020-10-27 | 新疆大学 | Black TiO2Preparation method of nanosheet photocatalyst |
| CN112915989A (en) * | 2021-01-27 | 2021-06-08 | 中国建筑材料科学研究总院有限公司 | SiO (silicon dioxide)2@TiO2Nano composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 殷锦捷 等: "新型苯乙烯–丁二烯–苯乙烯(SBS)防水涂料的制备", 《电镀与涂饰》, vol. 29, no. 08, pages 47 - 49 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115746652B (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101184815B (en) | Dispersion containing hollow SiO2, coating composition and substrate with antireflection coating film | |
| CN110896638B (en) | Self-cleaning coating, self-cleaning fiber, self-cleaning carpet and application thereof | |
| TW588017B (en) | Titanium-containing materials | |
| CN110317476B (en) | Nano functional coating and preparation method and application thereof | |
| CN103449735B (en) | A kind of nanometer hydrated calcium silicate super-hydrophilic thin film and preparation method thereof and application | |
| CN102164860A (en) | A photocatalytic nanocomposite material | |
| JP3755852B2 (en) | Coating liquid for forming transparent film having photocatalytic activity and substrate with transparent film | |
| CN112125335B (en) | Micro-nano titanium dioxide, preparation method and application | |
| CN104085165A (en) | Method for preparing titanium dioxide photocatalyst coating | |
| CN104692671A (en) | Preparation method of super-hydrophobic self-cleaning glass based on ZnO nano array coating | |
| JP2015116731A (en) | Substrate with repellent coating film and manufacturing method therefor | |
| JP6206418B2 (en) | Coating liquid and article for alkali barrier layer formation | |
| CN115746652A (en) | Coating with air purification and self-cleaning functions, coating and preparation method thereof | |
| CN109385122A (en) | A kind of preparation method of graphene doping self-cleaning glass coating liquid | |
| CN106381683A (en) | Preparation method of formaldehyde removing jacquard knitted fabric | |
| CN112194143A (en) | Preparation method of structural color-generating material with photocatalytic effect and stable structure | |
| JP3537110B2 (en) | Coating composition for forming transparent film having photocatalytic activity and substrate with transparent film | |
| CN114054009A (en) | Preparation method of composite titanium dioxide material with good formaldehyde removal function | |
| JP2015047530A (en) | Substrate having water-repellent transparent coating for water treatment and manufacturing method of the same | |
| CN107418432A (en) | A kind of method that leather stability and durability are improved based on nano titanium oxide | |
| WO2019090660A1 (en) | Method for preparing size-selective nano-mesoporous sio2-tio2 composite photocatalytic material | |
| CN110918079B (en) | Nano-powder titanium dioxide film acid-resistant material and preparation method thereof | |
| CN112266183B (en) | Titanium dioxide nanotube film, preparation method and glass attached with film | |
| CN107603316A (en) | A kind of preparation method of antifogging self-cleaning nano material | |
| JPH0648777A (en) | Ultraviolet ray absorbing film and its production |
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 |