CN111548694B - Preparation method of external wall thermal insulation coating with self-cleaning function - Google Patents
Preparation method of external wall thermal insulation coating with self-cleaning function Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
Abstract
The invention discloses a preparation method of an external wall thermal insulation coating with a self-cleaning function, which comprises the steps of adding P123 into absolute ethyl alcohol, stirring and dissolving to obtain a template agent solution; adding zirconium nitrate and butyl titanate into the template agent solution, stirring for 4-6 h at room temperature, adding titanium dioxide, mixing uniformly, and drying in a vacuum oven to obtain modified titanium dioxide; respectively adding a wetting agent, a dispersing agent, a flatting agent and a defoaming agent A under the stirring condition of deionized water, and stirring for 10-15 min; adding the modified titanium dioxide, the filler, the hollow glass beads and the aerogel silicon dioxide, and stirring for 20-25 min; adding the pure acrylic emulsion, the defoamer B, pH stabilizer and the film forming additive, and stirring for 10-15 min; and filtering, coating and drying to obtain the self-cleaning exterior wall thermal insulation coating.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of an external wall thermal insulation coating with a self-cleaning function.
Background
The building industry of China pushes the energy conservation of buildings to the utmost extent, namely, the utilization efficiency of heat energy is improved, and the energy waste is reduced, so that the living environment of people is effectively improved and the energy is saved. The building energy conservation not only needs to depend on the building design, but also takes the more important measure of developing and applying the heat-insulating material. The heat insulation performance of the heat insulation coating on the current market is generally poor, the heat insulation effect provided by a single coating is limited, the functions of the coatings are single, and the defects seriously limit the application of the exterior wall coating on the market.
The performance in recent years is also remarkable, and the reflective insulation coating also develops to a healthier and more correct direction. In this process, not only is it clear in concept: the use of the reflective pigment is an important means for improving the heat insulation performance of the colored exterior wall heat insulation coating, and the development of the exterior wall reflective heat insulation coating also needs to revise the relevant standards; and it is clear theoretically: simple' reflectionThe radiation mechanism is not possible to have a heat preservation effect, and the three mechanisms are combined to manufacture the high-quality reflective heat-insulation coating, so that guidance is provided for correctly evaluating and developing the energy-saving coating of the building outer wall. Super heat-insulating nano material-SiO2The aerogel is in a solid matter form, has a three-dimensional network framework and a unique nano structure, has the pore size and the particle diameter in the range of nano magnitude (1-100 nm), and has a high specific surface area (200-1000 m)2(g), high porosity (80-99.8%) and low density (0.002 g/cm)3) Low thermal conductivity [0.001W/(m X K)]And the like, and can be applied to heat-insulating coatings. On the other hand, in order to increase the high vacuum degree of the coating and the reflection capability of different sunlight wavelengths, the ceramic microspheres are compounded in grades, the formed heat insulation layer has high vacuum degree and strong heat insulation performance, the overlapping of materials is reduced when a thinner layer is formed, the performance is stable and is not easy to attenuate after the heat insulation film is formed, and the exterior wall coating with the self-cleaning function and the heat insulation performance is rarely reported in numerous documents.
Chinese patent CN107868530A discloses a building exterior wall heat-insulating coating, which combines styrene-acrylic emulsion with alkyd resin, so that a dried coating film has better transparency, the reflectivity of a filler is improved, the heat-insulating effect of the coating is improved, but the weather resistance and the aging resistance of the coating are weaker, the coating is easy to age and peel after long-term exposure, and the neatness and the attractiveness of the exterior wall surface cannot be ensured.
In recent years, cheap and easily available metal oxides are used as carriers for photocatalytic degradation of pollutants and pigments and fillers in paints, the metal oxides are mainly used for exciting free electrons under light to degrade specific organic matters due to large band gap energy, but the metal oxides in suspension are not easy to separate and are easy to run off, so that better fixation of the metal oxides on wall surfaces is a key point of research. Ren et al [ Ren Y, Li W, Cao Z, et al Robust TiO2nanorods-SiO2core-shell coating with high-performance self-cleaning properties under visible light[J].Applied Surface Science.2020,509:145377–145387]The titanium tetrachloride, the ethyl orthosilicate, the ammonia water, the hydrogen peroxide and the absolute ethyl alcohol are used as raw materials for preparationThe silicon dioxide/titanium dioxide self-cleaning coating has high self-cleaning efficiency and high visible light conversion rate, but the coating has good transmittance, is unfavorable for the heat preservation function and the like, and can achieve good heat preservation performance by modifying and modifying to change the permeability. Maurizio et al [ Maurizio S, Sina G, Alberto B, et al.Adsoration and photocatalytic degradation of VOCs by fluorinated ionic coating with TiO2nanopowders for air purifcation[J].Chemical Engineering Journal,2019,361:885–896.]The self-cleaning titanium dioxide coating with the internal fluoride hydrophobic layer and the external photosensitive layer is prepared by taking tetrafluoroethylene, sulfonyl fluoroether vinyl, propanol, commercial titanium dioxide and anatase as raw materials, the material is novel, the degradation conversion efficiency is high, the preparation process is complex, and the coating is only suitable for treating VOC gas in a room and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an external wall thermal insulation coating with a self-cleaning function, wherein the formed thermal insulation layer has high vacuum degree and high thermal insulation performance, the overlapping of materials is reduced when a thinner layer surface is formed, the performance is stable and is not easy to attenuate after a thermal insulation film is formed, and the thermal insulation is better.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of an external wall thermal insulation coating with a self-cleaning function comprises the following steps:
(1) adding a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) into absolute ethyl alcohol, stirring and dissolving to obtain a template agent solution; adding zirconium nitrate and butyl titanate into the template agent solution, stirring for 4-6 h at room temperature, adding titanium dioxide, mixing uniformly, and drying in a vacuum oven to obtain modified titanium dioxide;
(2) adding the wetting agent, the dispersing agent, the flatting agent and the defoaming agent A into deionized water under the stirring condition of 600-800r/min and stirring for 10-15 min; adding the modified titanium dioxide, the filler, the hollow glass beads and the aerogel silicon dioxide, and stirring for 20-25 min at the rotation speed of 1200-1400 r/min; adding pure acrylic emulsion, a defoamer B, pH stabilizer and a film forming additive, adjusting the rotating speed to 600-800r/min, and stirring for 10-15 min; and filtering, coating and drying to obtain the self-cleaning exterior wall thermal insulation coating.
Adding 200-250 parts by volume of deionized water into a container, respectively adding 0.5-1.0 part by mass of a wetting agent, 1.0-1.5 parts by mass of a dispersing agent, 1.3-1.7 parts by mass of a leveling agent and 1.5-2.0 parts by mass of an antifoaming agent under stirring at 800r/min for 600 plus materials, adding 50-100 parts by mass of modified titanium dioxide and 100-150 parts by mass of a common filler after stirring for 10-15 min, adding a certain amount of hollow glass beads and aerogel silica, adjusting the rotating speed to 1400r/min for 1200 plus materials, adding 100-150 parts by volume of a pure acrylic emulsion, 1.5-2.0 parts by mass of an antifoaming agent, 1.5-2.0 parts by mass of a pH stabilizer and 3.0-3.5 parts by mass of a film-forming auxiliary agent after stirring for 20-25 min, adjusting the rotating speed to 800r/min for stirring for 10-15 min, filtering, coating, and detecting the performance of the coating after drying.
According to the scheme, the raw materials in the step 1 are calculated according to the parts by weight as follows:
2.0-3.0 parts of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer; 3.0-8.0 parts of zirconium nitrate; 10 parts of butyl titanate; 24-30 parts of titanium dioxide; 40-55 parts of absolute ethyl alcohol.
According to the scheme, the raw materials in the step 2 are calculated according to the parts by weight as follows:
50-100 parts of modified titanium dioxide; 100-150 parts of pure acrylic emulsion; 100-150 parts of a filler; 45-55 parts of hollow glass beads; 0-10 parts of aerogel silicon dioxide; 0.5-1.0 part of wetting agent; 1.0-1.5 parts of a dispersing agent; 1.3-1.7 parts of a leveling agent; 1.5-2.0 parts of a defoaming agent A; 1.5-2.0 parts of a defoaming agent B; 1.5-2.0 parts of a pH stabilizer; 3.0-3.5 parts of a film-forming assistant; 200-250 parts of deionized water.
According to the scheme, in the step (1), the drying temperature is 40-55 ℃, and the drying time is 4-8 hours.
According to the scheme, the filler in the step (2) is any one or mixture of heavy calcium carbonate and talcum powder.
According to the scheme, in the step (2), the drying temperature is 30-35 ℃, and the drying time is 4-6 hours.
According to the invention, P123 is added into absolute ethyl alcohol to slowly form triblock micelles, zirconium ions and titanate ions generated by hydrolysis in solution are orderly fixed, and as the added titanium dioxide is a large number of rutile type spherical particles, the micelles can be combined with functional groups on the surfaces of titanium dioxide particles, a block copolymer can be removed after drying and evaporation treatment, and zirconium dioxide can be doped in a crystal structure of titanium dioxide, so that the band gap energy of the titanium dioxide is improved, and the photocatalytic activity of the titanium dioxide on pollutants is enhanced.
The hollow microspheres and the aerogel silicon dioxide are used as functional fillers and are coated on the surface of a solid under the coordination of various auxiliaries, so that a three-dimensional network hollow structure connected by the closed microspheres can be formed, solid heat transfer can only be transferred along a framework, heat conduction is effectively prevented, the formed heat insulation layer has high vacuum degree and strongest heat insulation performance, overlapping of materials is reduced when a thinner layer is formed, the formed heat insulation film has stable performance and is not easy to attenuate, and the heat insulation film has better heat insulation performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process is simple and the cost is low;
(2) through an experiment of simulating the pollutants of the outer wall by photodegradation of the pollutants in water, the photodegradation performance of the coating is greatly improved compared with that of the common outer wall coating, and the removal rate of MB and phenol solution under a certain condition reaches 91.2 percent and 89.5 percent; meanwhile, the coating prepared by the invention has excellent water resistance and can not fall off in a solution;
(3) the aerogel silicon dioxide added into the coating has larger heat conduction and heat resistance, so that the heat conduction coefficient of the coating is 0.030W/(m × K), the coating is superior to a large amount of coatings on the market, and the aging resistance of the coating is also better.
Drawings
FIG. 1: XRD patterns of the modified titanium dioxides obtained in examples 1 to 3;
FIG. 2: SEM images of the modified titanium dioxides obtained in examples 1 to 3;
FIG. 3: FT-IR spectra of exterior wall coatings obtained in examples 1-3;
FIG. 4: graph of the exterior wall coating obtained in example 1 versus contaminant degradation;
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1:
(1) adding 2.0g P123 to 45mL of absolute ethyl alcohol, stirring to dissolve, adding 5.5g of zirconium nitrate and 10.0g of butyl titanate into the template solution, stirring at room temperature for 5 hours, adding 30.0g of titanium dioxide, mixing uniformly, finally drying in a vacuum oven at 50 ℃ for 6 hours, and taking out to obtain modified titanium dioxide;
(2) adding 250mL of deionized water into a container, respectively adding 1.0g of wetting agent, 1.0g of dispersing agent, 1.7g of flatting agent and 2.0g of defoaming agent under stirring at 600r/min, adding 100g of modified titanium dioxide and 100g of heavy calcium carbonate after stirring for 15min, adding 50g of hollow glass microspheres and 10g of aerogel silicon dioxide, stirring and adjusting to 1200r/min, adding 120mL of pure acrylic emulsion, 1.5g of defoaming agent, 1.5g of pH stabilizer and 3.5g of film-forming assistant after stirring for 25min, then adjusting the rotating speed to 800r/min, stirring for 10min, filtering and drying to detect the performance of the coating, wherein the thickness of the coating is 0.8 mm.
By simulating the pollutants of the outer wall through photodegradation of the pollutants in water, the coating can not fall off in a solution and the photodegradation performance is greatly improved compared with that of a common outer wall coating, and the relationship between the surface density and the photocatalytic activity of the degraded methylene blue (a) and the degraded phenol (b) is shown in figure 4; under certain conditions, the optimal removal rate of the photodegradant on methylene blue and phenol solution is 91.2 percent and 89.5 percent respectively.
In addition, the aerogel silica added in the coating has larger heat conduction and heat resistance, and the heat conduction coefficient of the coating obtained in the embodiment is 0.030W/(m × K) through testing according to the GB/T25261-2010 standard, and the aging resistance is also better.
Example 2:
(1) adding 3.0g P123 to 40mL of absolute ethyl alcohol, stirring to dissolve, adding 3.0g of zirconium nitrate and 10.0g of butyl titanate into the template solution, stirring at room temperature for 4 hours, adding 24.0g of titanium dioxide, uniformly mixing, finally drying in a vacuum oven at 40 ℃ for 8 hours, and taking out to obtain modified titanium dioxide;
(2) adding 200mL of deionized water into a container, respectively adding 0.5g of wetting agent, 1.5g of dispersing agent, 1.3g of flatting agent and 1.5g of defoaming agent under stirring at 800r/min, adding 75g of modified titanium dioxide, 50g of heavy calcium carbonate and 50g of talcum powder after stirring for 10min, adding 55g of hollow glass microspheres, stirring and adjusting to 1400r/min, adding 150mL of pure acrylic emulsion, 2.0g of defoaming agent, 2.0g of pH stabilizer and 3.0g of film-forming assistant after stirring for 20min, then adjusting the rotating speed to 600r/min, stirring for 15min, filtering and drying to detect the performance of the coating, wherein the thickness of the coating is 0.6 mm.
Simulating the exterior wall pollutants by photodegrading the pollutants in the water, wherein the optimal removal rates of the photodegradant on methylene blue and phenol solution are 85.1% and 80.4% respectively under certain conditions; the aerogel silicon dioxide added into the coating has larger heat conduction and heat resistance, so that the heat conduction coefficient of the coating is 0.05W/(m × K), and the heat preservation performance is better.
Example 3:
(1) adding 2.0g P123 to 55mL of absolute ethyl alcohol by volume, stirring and dissolving, adding 8.0g of zirconium nitrate and 10.0g of butyl titanate into the template solution, stirring at room temperature for 6h, adding titanium dioxide, mixing uniformly, finally drying in a vacuum oven at 55 ℃ for 4h, and taking out to obtain modified titanium dioxide;
(2) adding 225mL of deionized water into a container, respectively adding 0.75g of wetting agent, 1.25g of dispersing agent, 1.5g of flatting agent and 1.8g of defoaming agent under stirring at 700r/min, stirring for 13min, adding 70g of modified titanium dioxide and 100g of talcum powder, adding 55g of hollow glass beads and 5.5g of aerogel silicon dioxide, stirring to adjust to 1300r/min, stirring for 23min, adding 100mL of pure acrylic emulsion, 1.8g of defoaming agent, 1.7gpH of stabilizer and 3.2g of film-forming assistant, then adjusting the rotating speed to 700r/min, stirring for 12min, filtering and drying to detect the performance of the coating, wherein the thickness of the coating is 0.5 mm.
Simulating the exterior wall pollutants by photodegrading the pollutants in the water, wherein the optimal removal rates of the photodegradant on methylene blue and phenol solution are 81.0% and 75.1% respectively under certain conditions; the aerogel silicon dioxide added into the coating has larger heat conduction and heat resistance, so that the heat conduction coefficient of the coating is 0.14W/(m × K).
FIG. 1 shows XRD patterns (corresponding to abc, respectively) of modified titanias obtained in examples 1 to 3, in which the modified titanias obtained by comparison are mainly a composite of rutile-type titanium dioxide and zirconium dioxide.
FIG. 2 is an SEM image of the modified titania obtained in examples 1-3 (each corresponding to abc), and the above modification process was compared to form a more efficient thermal insulation system with zirconia interposed between the two layers of titania.
FIG. 3 is a graph showing FT-IR spectra (corresponding to abc, respectively) of the exterior wall coatings obtained in examples 1-3, in which it was found that the components formed intimate chemical bonds, i.e., the components in the raw materials were mixed completely to form a stable material system.
In the above examples, the concentration of methylene blue and phenol was measured by UV spectrophotometry, and the UV visible spectrophotometer used was UVmini-1240 type of Shimadzu, Japan; measuring the infrared absorption peak of the functional group in the sample by adopting a Nexus type Fourier transform infrared spectrometer produced by Thermo Nicolet company in the United states; the phase parameters of the sample are calculated by a Sheer formula, and the X-ray diffractometer is an XRD-7000S/L instrument produced by Shimadzu; the scanning electron microscope photograph of the sample is obtained by taking a picture by a JSM-6510 scanning electron microscope of Japan K.K.; the thickness of the coating film is measured by a II type precision chromium plating vernier caliper produced by Wuhan teaching instrument factories.
It should be emphasized that the above-described embodiments are merely examples for clearly illustrating the present invention and are not to be considered as a complete limitation of the embodiments. Other variants will be apparent to those skilled in the art on the basis of the foregoing description, and it is not necessary to exemplify all the embodiments herein, but rather obvious variations are contemplated which are within the scope of the invention.
In the above embodiment, the removal rate W of the exterior wall coating to the contaminants is calculated by the following formula:
in the formula: c0 and Ct denote the initial concentration of Cr (VI) solution and the residual concentration of Cr (VI) solution at time t, mg L-1, respectively.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A preparation method of an external wall thermal insulation coating with a self-cleaning function is characterized by comprising the following steps:
(1) adding a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer into absolute ethyl alcohol, stirring and dissolving to obtain a template agent solution; adding zirconium nitrate and butyl titanate into the template agent solution, stirring for 4-6 h at room temperature, adding titanium dioxide, mixing uniformly, and drying in a vacuum oven to obtain modified titanium dioxide; the raw materials are as follows by weight: 2.0-3.0 parts of a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer; 3.0-8.0 parts of zirconium nitrate; 10 parts of butyl titanate; 24-30 parts of titanium dioxide; 40-55 parts of absolute ethyl alcohol;
(2) adding the wetting agent, the dispersing agent, the flatting agent and the defoaming agent A into deionized water under the stirring condition of 600-800r/min and stirring for 10-15 min; adding the modified titanium dioxide, the filler, the hollow glass beads and the aerogel silicon dioxide, and stirring for 20-25 min at the rotation speed of 1200-1400 r/min; adding pure acrylic emulsion, a defoamer B, pH stabilizer and a film forming additive, adjusting the rotating speed to 600-800r/min, and stirring for 10-15 min; and filtering, coating and drying to obtain the self-cleaning exterior wall thermal insulation coating.
2. The preparation method of the self-cleaning exterior wall thermal insulation coating as claimed in claim 1, wherein the raw materials in the step 2 are as follows by weight:
50-100 parts of modified titanium dioxide; 100-150 parts of pure acrylic emulsion; 100-150 parts of a filler; 45-55 parts of hollow glass beads; 0-10 parts of aerogel silicon dioxide; 0.5-1.0 part of wetting agent; 1.0-1.5 parts of a dispersing agent; 1.3-1.7 parts of a leveling agent; 1.5-2.0 parts of a defoaming agent A; 1.5-2.0 parts of a defoaming agent B; 1.5-2.0 parts of a pH stabilizer; 3.0-3.5 parts of a film-forming assistant; 200-250 parts of deionized water.
3. The preparation method of the self-cleaning exterior wall thermal insulation coating as claimed in claim 1, wherein the drying temperature in the step (1) is 40-55 ℃, and the drying time is 4-8 h.
4. The method for preparing an exterior wall thermal insulation coating with a self-cleaning function as claimed in claim 1, wherein the filler in the step (2) is any one or mixture of ground calcium carbonate and talcum powder.
5. The preparation method of the self-cleaning exterior wall thermal insulation coating as claimed in claim 1, wherein the drying temperature in the step (2) is 30-35 ℃ and the drying time is 4-6 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560078A (en) * | 2009-05-21 | 2009-10-21 | 北京虹霞正升涂料有限责任公司 | External wall heat-insulating coating |
| CN102380385A (en) * | 2011-09-26 | 2012-03-21 | 浙江工业大学 | Supported metal doped mesoporous titanium dioxide photocatalyst and application thereof |
| CN106978026A (en) * | 2017-03-21 | 2017-07-25 | 海安南京大学高新技术研究院 | Aerosil insulation emulsion paint and preparation method thereof |
| CN111171658A (en) * | 2020-02-11 | 2020-05-19 | 荆门市诺维英新材料科技有限公司 | Energy-saving and environment-friendly heat-insulating coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560078A (en) * | 2009-05-21 | 2009-10-21 | 北京虹霞正升涂料有限责任公司 | External wall heat-insulating coating |
| CN102380385A (en) * | 2011-09-26 | 2012-03-21 | 浙江工业大学 | Supported metal doped mesoporous titanium dioxide photocatalyst and application thereof |
| CN106978026A (en) * | 2017-03-21 | 2017-07-25 | 海安南京大学高新技术研究院 | Aerosil insulation emulsion paint and preparation method thereof |
| CN111171658A (en) * | 2020-02-11 | 2020-05-19 | 荆门市诺维英新材料科技有限公司 | Energy-saving and environment-friendly heat-insulating coating and preparation method thereof |
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