WO2013107081A1 - 一种二氧化钒智能温控涂层 - Google Patents
一种二氧化钒智能温控涂层 Download PDFInfo
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- WO2013107081A1 WO2013107081A1 PCT/CN2012/072021 CN2012072021W WO2013107081A1 WO 2013107081 A1 WO2013107081 A1 WO 2013107081A1 CN 2012072021 W CN2012072021 W CN 2012072021W WO 2013107081 A1 WO2013107081 A1 WO 2013107081A1
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- C08K3/22—Oxides; Hydroxides of metals
Definitions
- the invention relates to an intelligent temperature control coating for vanadium dioxide, which has the advantages of small thickness, high precision, high transparency, low haze, good adhesion and outstanding aging resistance, and is mainly used for preparing glass film for building doors and windows. , automotive glass or industrial metal containers and other occasions.
- China's building energy consumption has accounted for 27.8% of total social energy consumption, of which heating and air conditioning consumes 55% of total building energy consumption. .
- the proportion of glass in the outer wall is increasing. It is estimated that the heat transfer through the glass window accounts for 48% and 71% respectively in the winter and summer. If the air conditioner is used to adjust the indoor temperature, the cooling temperature is increased by 2 °C, the cooling load is reduced by about 20%; the heating temperature is lowered by 2 °C, and the heating load is reduced by about 30%.
- the energy consumption can be greatly reduced by attaching a heat-insulating film to the glass or applying a heat-insulating coating.
- the thermal insulation film or coating on the market mainly relies on blocking infrared performance and cannot respond to environmental changes. They only have the function of reflecting infrared light, but they do not transmit infrared rays at low temperatures, and cannot intelligently adjust indoor and outdoor.
- the role of temperature difference it is necessary to find a material that can intelligently adjust the heat of the sun, so as to achieve the role of warm winter and cool summer.
- the vanadium dioxide material has a first-order phase change characteristic, which can sense the change of the ambient temperature, and the change of the intelligent response realizes selective transmission or shielding of the solar light band.
- the vanadium dioxide-containing film or coating is almost completely transparent to visible and mid-infrared light in sunlight; when the temperature exceeds the vanadium dioxide semiconductor -
- the metal phase transition temperature the vanadium dioxide undergoes a phase change and is converted into an R phase. At this time, the material can selectively block the mid-infrared light to achieve transparent (visible light transmission) heat resistance.
- Vanadium dioxide semiconductor - Metal phase transition is a thermally induced reversible change, and its temperature switching effect can be used to intelligently control the switching of mid-infrared rays.
- the use of vanadium dioxide in the low transmission of high temperature in the infrared region and high transmission at low temperatures can produce a completely intelligent energy-saving window system.
- An intelligent temperature-controlled coating can be prepared by making the vanadium dioxide material nano-sized and compounded with the organically modified material.
- agglomeration easily occurs between the particles.
- the vanadium dioxide nanoparticles can be directly added to the coating, it is difficult to truly exert the performance of the nano material, and it is easy to agglomerate, affecting the optical properties and appearance of the coating, thereby limiting the application of the material on the glass film and the transparent glass.
- a vanadium dioxide smart temperature control coating is mentioned in Chinese Patent Application No.
- vanadium dioxide particles mentioned therein belong to unmodified vanadium dioxide particles, and do not involve pretreatment of particles, especially the present invention.
- the vanadium dioxide particles are subjected to a pre-dispersion treatment, in particular, an organic modification treatment for improving the dispersibility and chemical stability properties.
- Chinese Patent Application No. 200810033032.6 mentions a smart thermal insulation film and a preparation method thereof, but it does not perform organic modification pre-dispersion treatment on VO 2 particles, especially the present invention, and the present invention will organically modify the second After the vanadium oxide powder modification treatment, especially after the silane coupling agent treatment, the powder dispersibility is greatly improved, and the performance of the nano material is truly exerted, which is close to the theoretical calculation result, and the prepared intelligent temperature control coating pair The regulation performance of infrared light is significantly improved, which is close to the theoretical calculation results.
- Cida Patent Application No.: CN101265374A Disclosed is a vanadium dioxide solar thermal intelligent temperature control high polymer film which is prepared by directly adding vanadium dioxide to a polymer film, and the invention is prepared by a coating method, and the coating prepared by the invention The layer has higher transparency, smaller haze and better performance.
- vanadium dioxide powder and vanadium dioxide powder and other materials to prepare a film, the method is simple, easy to operate on a large scale, not only can be used for energy-saving transformation of the original glass window, and can be coated on different substrates, Expand the applicability of vanadium dioxide.
- the vanadium dioxide powder is prepared into a vanadium dioxide slurry to form a film and a coating, the vanadium dioxide powder is required to have excellent dispersing properties and chemical stability. .
- the present invention provides a vanadium dioxide composite powder comprising a vanadium dioxide nanometer powder having a chemical composition of V 1-x M x O 2 , and an organically modified long-chain molecule on the surface of the vanadium dioxide nano powder.
- M is a doping element, 0 ⁇ x ⁇ 0.5.
- the vanadium dioxide composite powder of the invention is organically modified on the surface of vanadium dioxide and its doped nano powder. It is different from the generally unmodified or inorganically encapsulated and modified vanadium dioxide powder.
- the surface of the vanadium dioxide is connected to the organically modified long-chain molecule by means of an organic modifier, thereby greatly increasing the vanadium dioxide powder.
- the vanadium dioxide composite powder provided by the invention has good stability and dispersibility, can be stored for a long time, can be used as a smart heat insulating powder for preparing intelligent energy-saving coatings or coatings, and can also be used for heat insulation of glass and exterior walls. occasion. Unlike general insulation materials, it can block infrared light significantly above the phase transition temperature, while infrared rays can be highly transmitted below the phase transition temperature, and this change is reversible, enabling intelligent adjustment of solar heat.
- the content of the organically modified long-chain molecule is 0.1 to 50%. . More preferably, the organic modified long chain molecular content is from 1 to 10% . If the molecular content of the organic modified long chain is too small, the full surface of the powder cannot be fully encapsulated; if the organic modified long chain molecular content is too large, the organic molecules will entangle each other, which will affect the dispersion effect.
- the organically modified long chain molecular chain has a length of from 0.1 nm to 100 nm.
- the invention relates to the organic surface modification of vanadium dioxide nanoparticles, which can effectively improve the dispersibility of vanadium dioxide and its doped nano powder and the chemical stability of the powder. .
- the organically modified long-chain molecule is composed of a long-chain alkyl group, a polyacrylic acid group, a polyvinyl alcohol group, an epoxy group, a long-chain alkylamine group, a halogenated long-chain alkyl group, a carboxylated long-chain alkyl group, or the like. Functionalized organic long chain .
- the vanadium dioxide composite powder of the invention is coated on the surface of the vanadium dioxide powder by grafting the organic modification modifier on the surface of the vanadium dioxide powder, thereby changing the surface characteristics of the vanadium dioxide, according to the selection
- the difference in groups can increase the dispersion of vanadium dioxide composite particles in different solvents, and expand the use of vanadium dioxide particles in intelligent temperature-controlled coatings or coatings.
- the vanadium dioxide nano powder in the vanadium dioxide composite powder of the present invention is a rutile phase, and the phase transition temperature is -20 to 70. °C adjustable.
- the rutile phase of vanadium dioxide can account for up to 80%, or even 100%.
- the vanadium dioxide nano powder has a first-order phase change characteristic, can sense the change of the ambient temperature, and the smart response can realize the selective transmission or shielding of the solar light band.
- the vanadium dioxide-containing film or coating is almost completely transparent to visible and mid-infrared light in sunlight; when the temperature exceeds the vanadium dioxide semiconductor -
- the vanadium dioxide undergoes a phase change and is converted into an R phase.
- the material can selectively block the mid-infrared light to achieve transparent (visible light transmission) heat resistance.
- Vanadium dioxide semiconductor - Metal phase transition is a thermally induced reversible change, and its temperature switching effect can be used to intelligently control the switching of mid-infrared rays.
- the doping element M specified in the present invention may be 21 to 30 near vanadium in the periodic table.
- 21 to 30 near vanadium in the periodic table The transition elements include tantalum, titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, and the tin and its nearby elements include indium, antimony, tin, gallium, antimony, lead, and antimony.
- Preferred doping elements are tungsten, molybdenum, niobium, tin, iron, zinc and titanium.
- the size and morphology of the doped vanadium dioxide powder can be controlled, and the doping elements used can also regulate the phase transition temperature of vanadium dioxide.
- the doped vanadium dioxide powder is preferably in the form of particles, and the aspect ratio of the particles is from 1:1 to 10:1, preferably 1:1. 5:1, more preferably 1:1 to 2:1.
- the particle size is no more than 1 um in at least one dimension, preferably no more than 100 nm in at least one dimension, more preferably no greater than three dimensions 100 nm, most preferably no more than 70 nm in all three dimensions.
- the granules may be, for example, a nearly spherical shape, an elliptical shape, a snowflake shape, a cuboid shape, a sheet shape, or the like.
- the vanadium dioxide powder having the above size and morphology has better dispersibility.
- the dispersibility of the modified composite powder will be further improved.
- the present application also provides a method for preparing a vanadium dioxide composite powder, comprising the steps of: (1) dispersing a vanadium dioxide nano powder in a dispersion medium to obtain a mixture A (2) adding a dispersing aid and an organic modifier for forming an organically modified long-chain molecule on the surface of the vanadium dioxide powder in the mixture A, stirring until fully mixed to obtain a mixture B; (3) mixing the mixture B Drying produces an organically modified vanadium dioxide composite powder.
- the vanadium dioxide powder may be rutile phase vanadium dioxide nanoparticles or doped rutile phase vanadium dioxide nanoparticles. Can be based on public patents
- the preparation method provided by 2010PA011267CN may also be rutile phase vanadium dioxide nanoparticles prepared by other known methods or doped rutile phase vanadium dioxide nanoparticles.
- the powder particle size is preferably 200nm the following.
- the morphology of the powder can be particles, nanorods and snowflake particles.
- the precursor (the tetravalent vanadium ion aqueous solution) can be treated with an alkaline reagent before the doping element, and the size and morphology of the vanadium dioxide powder can be controlled. At least one dimension is not greater than 1um) and morphology (granular, length to diameter ratio not greater than 10:1
- the prepared vanadium dioxide powder has a small crystal grain size, uniform particle size, and stable crystal form, and has good dispersibility in water and a dispersant (for example, polyvinylpyrrolidone), and is easily coated on a substrate such as glass.
- a dispersant for example, polyvinylpyrrolidone
- the preparation method of the vanadium dioxide composite powder provided by the invention, the dispersing aid added in the step (2) may be polyvinyl alcohol, polyvinylpyrrolidone, organic modified polysiloxane dipropylene glycol monomethyl ether solution, One or more of a silicone surfactant or a fluorosurfactant or a dispersion aid well known in the art.
- the organic modifier added in the step (2) may be an organic modifier such as stearic acid, polyacrylic acid, a silane coupling agent, an aluminate coupling agent or a titanate coupling agent.
- a silane coupling agent containing a long polymer chain is preferred.
- the surface of the vanadium dioxide can be connected to the organic long-chain molecules by means of a coupling agent, thereby greatly improving the chemical stability and dispersibility of the vanadium dioxide powder.
- the dispersion medium used in the preparation method of the vanadium dioxide composite powder provided by the present invention may be an inert solvent such as ethanol, isopropanol, chloroform, dimethylformamide, dimethyl sulfoxide dichloroethane or acetone. One or several.
- Organic modification in an inert medium prevents the vanadium dioxide from denaturation and improves the chemical stability of the powder.
- the preparation method of the vanadium dioxide composite powder provided by the invention, the preparation process innovation, the vanadium dioxide (vanadium dioxide) can be effectively improved by the organic surface modification process of the organic modifier And the dispersibility and chemical stability of the doped nanopowder.
- the present invention provides a vanadium dioxide powder slurry comprising the vanadium dioxide composite powder of the present invention.
- the vanadium dioxide powder slurry provided by the present invention may comprise (1) a vanadium dioxide composite powder comprising vanadium dioxide nano powder having a chemical composition of V 1-x M x O 2 , and The surface of the powder is connected to an organically modified long-chain molecule, wherein M is a doping element, 0 ⁇ x ⁇ 0.5; and (2) a dispersion medium.
- the weight ratio of the vanadium dioxide composite powder to the dispersion medium may be 1:1 ⁇ 1:1000 .
- the weight ratio of the vanadium dioxide composite powder to the dispersion medium is 1:10 to 1:100.
- the vanadium dioxide composite powder prepared by the invention is 0-50% by weight Can be effectively dispersed within the scope. From the point of view of the application of the smart coating, a range of 1 to 10% by weight is more preferable. If the content is too high, it will affect the light transmittance of the coating. If it is too low, it will be difficult to exert the intelligent heat insulation effect of the coating.
- one or more of deionized water, ethanol, propanol, isopropanol, ethyl acetate, toluene, and methyl ethyl ketone may be selected as the dispersion medium in the vanadium dioxide powder slurry of the present invention.
- the vanadium dioxide composite powder slurry of the present invention may further comprise a dispersing aid, which may be selected from the group consisting of polyacrylate, polyacrylamide, polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone, One or more of polyester, modified polyurethane and modified acrylic dispersant .
- a dispersing aid which may be selected from the group consisting of polyacrylate, polyacrylamide, polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone, One or more of polyester, modified polyurethane and modified acrylic dispersant .
- the present invention further provides an intelligent temperature-controlled coating of vanadium dioxide formed by mixing a vanadium dioxide powder slurry, a polymer emulsion and a coating aid of the present invention onto a substrate.
- the vanadium dioxide composite powder in the vanadium dioxide intelligent temperature control coating provided by the invention has a solid content of 0.1 to 50%. Preferably 2%-20% .
- the vanadium dioxide composite powder in the vanadium dioxide intelligent temperature control coating can effectively form a film in a solid content of 0.1 to 50%. From the application point of view, solid content Too high will affect the light transmittance of the coating. If it is too low, it will be difficult to exert the intelligent insulation effect of the coating.
- the dry film thickness of the vanadium dioxide intelligent temperature control coating provided by the invention is 0.05 ⁇ 50 u m. Preferably 0.5 ⁇ 10 u m ;
- the temperature control coating can be applied by spraying, scraping, brushing, showering or roller coating.
- the coating method is generally adopted, and the coating thickness can be according to the coating roller.
- the mesh size and the solid content of the coating solution are adjusted, and the advanced roll coating technique can be used to minimize the dry film thickness. 0.05 u m.
- the vanadium dioxide composite powder of the present invention and a vanadium dioxide powder slurry comprising the powder, It can be applied to the preparation of intelligent energy-saving coatings or coatings.
- the prepared coatings have high transparency, low haze and strong aging resistance. They are mainly used in flexible materials such as films and braids, and can also be used in heat insulation applications such as glass and exterior walls.
- Figure 1 is a transmission electron micrograph of vanadium dioxide powder with no organic modification on the surface of vanadium dioxide powder
- Figure 2 is a transmission electron micrograph of the organically modified vanadium dioxide composite powder on the surface of vanadium dioxide powder
- image 3 The high and low temperature graph of the vanadium dioxide intelligent temperature control coating in one example of the present invention; the high temperature and low temperature graph of the intelligent temperature control coating prepared by using the vanadium dioxide composite powder of the invention and the slurry thereof ;
- Figure 4 is a high and low temperature graph of an intelligent temperature-controlled coating prepared from vanadium dioxide powder without organic modification.
- the vanadium dioxide nano powder is dispersed in a dispersion medium to obtain a mixture A.
- the method for preparing the above-mentioned vanadium dioxide composite powder specifically, the vanadium dioxide powder having a weight percentage of 0.1 to 50% and 50 ⁇ 99% of the dispersion medium is stirred and mixed at a high speed, and the mixture is ultrasonically dispersed, and then a dispersing aid and an organic modifier are added to the mixture at a constant temperature of 0 to 200. Stir at °C, disperse by ultrasonic, sanding or ball milling, and then centrifuge to precipitate, and vacuum dry at a certain temperature to obtain an organically modified vanadium dioxide composite powder.
- the weight ratio of the vanadium dioxide nanopowder to the dispersion medium may be 1:1 ⁇ 1:20.
- the weight ratio of the vanadium dioxide nanopowder to the dispersion medium is 1:1 to 1:10. More preferably 1:2 to 1:5 .
- the weight ratio is too small, the probability of contact of the vanadium dioxide powder with the organic modifier is low, and a long dispersion time and a large amount of modifier are required; if the weight ratio is too large, the powder is not suitable for the dispersion medium. Fully dispersed and wetted, affecting the later modification effect.
- the organic modifier may be an organic modifier such as stearic acid, polyacrylic acid, a silane coupling agent, an aluminate coupling agent or a titanate coupling agent.
- a silane coupling agent containing a long polymer chain is preferred.
- the amount of the organic modifier added to the mixture can be 0.05 to 5 wt%; preferably 0.1 to 2 wt% . If the molecular content of the organic modified long chain is too small, the full surface of the powder cannot be fully encapsulated; if the organic modified long chain molecular content is too large, the organic molecules will entangle each other, which will affect the dispersion effect.
- the surface of the vanadium dioxide can be connected to the organic long-chain molecules by means of a coupling agent, thereby greatly improving the chemical stability and dispersibility of the vanadium dioxide powder.
- the dispersing aid used may be one of polyvinyl alcohol, polyvinylpyrrolidone, organomodified polysiloxane dipropylene glycol monomethyl ether solution, silicone surfactant or fluorosurfactant or a dispersion agent well known in the art. kind or several.
- the dispersing aid is mainly used to reduce the surface tension of the solution and improve the wetting of the solvent on the surface of the powder, thereby improving the dispersion effect.
- the amount of the dispersing aid added to the mixture can be 0.02 to 2% by weight; preferably 0.05 to 1% by weight . Very little addition can achieve the desired dispersion. Adding too much will affect the surface organic modification process of the powder.
- the method for preparing the vanadium oxide powder slurry provided by the present invention may be 0.1 to 50%
- the vanadium dioxide powder is added to 40 to 99% of the dispersion medium, pre-dispersed by high-speed stirring, and then a dispersing aid is added to the mixture, and the uniformly mixed vanadium dioxide powder slurry is obtained by high-speed stirring.
- the slurry may be uniformly mixed by a dispersion method such as ultrasonication, ball milling, and/or sanding.
- the high-speed stirring speed can be 1000 to 3000 rad/min.
- Ultrasonic power can range from 50 to 5000 W with a frequency of 21 KHz.
- the ball mill speed can be selected from 10 to 2000 Rad/min.
- the speed of the sander can be from 10 to 2000 rad/min.
- the grinding medium can be selected from zirconia balls with a particle size of 0.02mm to 50mm. Preferably, it is a grinding medium having a small particle size.
- the intelligent temperature control coating of the invention is formed by mixing the vanadium dioxide powder slurry, the polymer emulsion and the coating auxiliary agent of the invention and coating on the substrate. . Specifically, 10 to 60% by weight of the vanadium dioxide powder slurry of the present invention may be added, and 20 to 80% by weight of the polymer emulsion is added thereto, and then a total of 0.01 to 5% by weight is added. Coating additives, such as wetting aids, filming aids, leveling agents, defoamers, and / Or a thickener, stirred at a high speed for a suitable period of time to obtain a mixed solution (coating) for forming a coating.
- Coating additives such as wetting aids, filming aids, leveling agents, defoamers, and / Or a thickener
- the substrate may be polypropylene ( PP), polyethylene (PE), polyamide (PA), polyvinyl chloride (PVC), polyethylene terephthalate (PET) and polymethyl methacrylate (PMMA) Plastic film of materials such as fibers or woven bags made of these materials.
- PP polypropylene
- PE polyethylene
- PA polyamide
- PVC polyvinyl chloride
- PET polyethylene terephthalate
- PMMA polymethyl methacrylate
- the filming aid in the coating assistant may be one or more of ethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, propylene glycol monobutyl ether, ethylene glycol propyl ether, dipropyl ether.
- ethylene glycol monobutyl ether propylene glycol monobutyl ether, dipropylene glycol methyl ether ether ester, propylene glycol monobutyl ether, ethylene glycol propyl ether, dipropyl ether.
- the wetting assistant in the coating aid may be one or more of lauryl sulfate, dodecylsulfonate, polyvinyl alcohol, polyvinylpyrrolidone, an organosilicon compound, and an organic fluorine compound.
- the antifoaming agent in the coating assistant may be one or more of dimethyl silicone oil, ether ester compound, modified mineral oil, polyoxyethyl glyceryl ether, small molecular metal organic and modified silicone polymer.
- the leveling agent in the coating aid may be one or more of ethylene glycol butyl ether, acetobutyl cellulose, polyacrylate, silicone oil, and modified silicone compound.
- the thickener in the coating aid may be a cellulose thickener, a polyethylene wax, a fumed silica, a polyacrylic thickener, or an associative polyurethane thickener.
- UV absorbers such as benzophenone and its derivatives, o-hydroxyphenylbenzotriazole and its derivatives, aromatic ester compounds or hydroxyphenyl-s-triazine and its derivatives can be used as coatings in the present invention. Use of UV absorbers.
- Figure 1 is a transmission electron micrograph of vanadium dioxide powder with no organic modification on the surface of vanadium dioxide powder; Referring to Fig. 1, the morphology of the vanadium dioxide nanopowder particles without organic modification, the particle size of the powder varies from 10 to 100 nm, and the agglomerated particles are present but the particles are relatively loose.
- Figure 2 is a transmission electron micrograph of the organically modified vanadium dioxide composite powder on the surface of vanadium dioxide powder; see Figure 2, Morphology of organic surface modified vanadium dioxide composite powder, powder particle size 10 ⁇ 100nm The powders are slightly larger in particle size than the non-organic modified particles because the surface is coated with organic groups, but the powders are dispersed.
- FIG. 3 is an example of the present invention (Embodiment 1 High-low temperature curve of the intelligent temperature-controlled coating of vanadium dioxide; is a high-temperature curve of the intelligent temperature-controlled coating prepared by using the vanadium dioxide powder of the invention and the slurry thereof;
- the visible transmittance of the coating in this embodiment is low 53.3%, high temperature 51.8%, solar energy transmittance 57%, high temperature 43.6%, coating phase transition temperature 40 °C, high and low temperature solar energy regulation efficiency can reach 13.4%
- the high-low temperature infrared integral adjustment rate is 24.2%, and the high-low temperature infrared light 1500nm transmittance difference can reach 36.8%.
- Figure 4 shows the high and low temperature curves of an intelligent temperature-controlled coating prepared without modified vanadium dioxide (Comparative Example 6) ), it is coated with an organic modified vanadium dioxide ( Figure 3 The difference is that since the modified vanadium dioxide powder is not used, its dispersibility is not good, causing the high temperature curve to be lower than the low temperature curve in the visible light portion, and the coating high temperature curve prepared by using the modified vanadium dioxide powder is The visible light portion is higher than the low temperature curve. And the visible light transmittance and infrared control performance are lower than those prepared by using modified vanadium dioxide powder (Fig. 3).
- each component is as follows: vanadium dioxide nano powder (doped tungsten, particle size 20 ⁇ 100 nm), 20g; ethanol (dispersion medium), 80 g; silane coupling agent (containing polyvinyl alcohol group, organic modifier), 1 g; polyvinylpyrrolidone (dispersion aid), 0.05 g.
- vanadium dioxide nano powder and dispersion medium are in 1500 Stir at rad/min for 30 min at high speed, and ultrasonically disperse for 30 min. Add the dispersing aid and silane coupling agent to it, and stir at a constant temperature of 70 °C for 2 h on a high-speed mixer. Then, the precipitate was centrifuged and dried under vacuum at 60 ° C to obtain a vanadium dioxide composite powder modified by a silicone coupling agent.
- each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 4 g; deionized water, 95.5 g; Modified acrylic dispersant, 0.5 g.
- the organically modified nano-powder was added to deionized water for high-speed stirring and pre-dispersion for 5 min, then dispersing agent was added for ultrasonic dispersion for 60 min, and stirred on a high-speed mixer for 2 h. , a vanadium dioxide composite powder slurry is obtained.
- the main properties of the vanadium dioxide composite powder and its slurry obtained in this example are shown in Table 1.
- the percentage of each raw material in mass is: Polymer emulsion (polyurethane emulsion): 40%; vanadium dioxide powder slurry prepared in the second embodiment of the present invention (solid content: 4%): 30%; deionized water: 28%; film-forming auxiliary agent (propylene glycol monobutyl ether): 0.5 %; Wetting assistant (polyvinyl alcohol): 0.2%; leveling agent (polyacrylate): 0.25%; defoamer (modified silicone compound): 0.25 %; thickener (cellulose thickener) ): 0.4%; UV absorber (hydroxyphenyl s-triazine derivative): 0.5%.
- each component is as follows: vanadium dioxide nano powder (undoped, particle size 20 ⁇ 60 nm), 10g; ethanol (dispersion medium), 90 g; silane coupling agent (containing long-chain alkylamino group, organic modifier), 1 g; polyvinyl alcohol (dispersing aid), 0.05 g.
- the vanadium dioxide nano powder and dispersion medium are in 1500 Stir at rad/min for 30 min at high speed and ultrasonically disperse for 30 min, then add dispersing aid and stearic acid to it, and stir at a constant temperature stirrer at 60 °C for 2 h. Further, the precipitate was centrifuged, and vacuum dried at 60 ° C to obtain a vanadium dioxide nanocomposite powder having a long-chain alkylamino group.
- each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 5 g; deionized water, 94.5 g; Polyacrylate dispersant, 0.05 g.
- the organically modified nano-powder was added to deionized water for high-speed stirring and pre-dispersed for 10 min, then dispersed with dispersing agent for 30 min, and stirred on a high-speed mixer.
- a vanadium dioxide composite powder slurry is obtained.
- the main properties of the vanadium dioxide composite powder and its slurry obtained in this example are shown in Table 1.
- the mass percentage of each raw material is: polymer emulsion (polyurethane emulsion): 60%; The vanadium dioxide powder slurry prepared in the second embodiment of the present invention (solid content: 5%): 30%; deionized water: 8.5 %; film-forming auxiliary agent (propylene glycol monobutyl ether): 0.25%; Wetting aid (polyvinyl alcohol): 0.1%; leveling agent (polyacrylate): 0.15%; defoamer (modified silicone compound): 0.25 %; thickener (associative polyurethane) Thickener): 0.35%; UV absorber (o-hydroxyphenylbenzotriazole derivative): 0.4 %.
- vanadium dioxide intelligent temperature control coating Adding an acrylic emulsion and deionized water to the vanadium dioxide powder slurry, and then adding a wetting assistant, a film forming aid, a leveling agent, an antifoaming agent, a UV absorber and a thickener at 1500 rad/min. High speed stirring 1h, get vanadium dioxide intelligent temperature control coating.
- the obtained vanadium dioxide intelligent temperature control coating is applied to PET by roll coating, and the coating thickness is controlled at 2.5 microns.
- the basic performance of the obtained intelligent temperature control coating is shown in Table 2. .
- each component is as follows: vanadium dioxide nano powder (doped tungsten, particle size 20 ⁇ 100 nm), 15 g; isopropyl alcohol (dispersion medium), 85 g; silane coupling agent (containing epoxy functional group, organic modifier), 1 g; organically modified polysiloxane dipropylene glycol monomethyl ether solution (dispersing aid), 0.08g.
- the vanadium dioxide nanopowder and the dispersion medium are firstly stirred at a high speed of 1000 rad/min for 20 min, and ultrasonically dispersed for 60 min.
- a dispersing aid and a silane coupling agent are added thereto, and stirred at a constant temperature of 80 ° C for 2 h on a high-speed mixer, and then centrifuged, 60 Vacuum drying at ° C gave vanadium dioxide nanocomposite powder with epoxy functional groups attached to it.
- each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 1.5 g; deionized water, 98 g; Modified polyester dispersant, 0.5 g.
- the organically modified nano-powder was added to deionized water for high-speed stirring and pre-dispersion for 5 min, then dispersing agent was added for ultrasonic dispersion for 20 min, and stirred on a high-speed mixer for 1 h. , a vanadium dioxide composite powder slurry is obtained.
- the main properties of the vanadium dioxide composite powder and its slurry obtained in this example are shown in Table 1.
- the mass percentage of each raw material is: polymer emulsion (acrylic emulsion): 45%; The vanadium dioxide powder slurry prepared in the second embodiment of the present invention (solid content: 1.5%): 45%; deionized water: 5%; film-forming auxiliary (diphenyl ether): 0.5%; Additives (organosilicon compounds): 0.2%; leveling agent (modified organosilicon compound): 0.25%; defoamer (small molecule metal organic): 0.25 %; thickener (associative polyurethane thickener): 0.8%; UV absorber (o-hydroxyphenylbenzotriazole derivative): 0.5%.
- vanadium dioxide intelligent temperature control coating Adding an acrylic emulsion and deionized water to the vanadium dioxide powder slurry, and then adding a wetting assistant, a film forming aid, a leveling agent, an antifoaming agent, a UV absorber and a thickener at 2500 rad/min. Stirring at high speed for 3h , get vanadium dioxide intelligent temperature control coating.
- the obtained vanadium dioxide intelligent temperature control coating is applied to PET by spraying, and the coating thickness is controlled at 6.5 micrometers.
- the basic performance of the obtained intelligent temperature control coating is shown in Table 2. .
- vanadium dioxide nano powder (doped with molybdenum, particle size 20 ⁇ 100 nm), 25 g; Isopropanol (dispersion medium), 75 g; titanate coupling agent (containing epoxy group, organic modifier), 1 g; polyvinyl alcohol (dispersion aid), 0.15 g.
- vanadium dioxide nano powder and dispersion medium Disperse and disperse for 20 min at 1500 rad/min, and ultrasonically disperse for 60 min, then add dispersing aid and titanate coupling agent, and stir at a constant temperature of 80 °C on a high-speed mixer. 2 h, the precipitate was centrifuged again, and dried under vacuum at 70 ° C to obtain a vanadium dioxide nanocomposite powder with an epoxy group attached to the surface.
- each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 3 g; deionized water, 96.95 g; Modified acrylic dispersant, 0.05 g.
- the organically modified nano-powder was added to deionized water for high-speed stirring and pre-dispersion for 5 min, then dispersing agent was added for ultrasonic dispersion for 30 min, and stirred on a high-speed mixer for 1 h. , vanadium dioxide and its doped nano powder slurry are obtained.
- the main properties of the vanadium dioxide composite powder and its slurry obtained in this example are shown in Table 1.
- the mass percentage of each raw material is: polymer emulsion (acrylic emulsion): 50%; The vanadium dioxide powder slurry prepared in the second embodiment of the present invention (solid content: 3%): 30%; deionized water: 18.5%; film-forming auxiliary (ethylene glycol monobutyl ether): 0.2% ; Wetting assistant (organosilicon compound): 0.05%; leveling agent (butyl acetate): 0.2%; defoamer (modified mineral oil): 0.35 %; thickener (polyacrylic thickener) : 0.2%; UV absorber (benzophenone derivative): 0.5%.
- each component is as follows: vanadium dioxide nano powder (doped tungsten, particle size 20 ⁇ 100 nm), 5 g; isopropanol (dispersion medium), 95 g; aluminate coupling agent (containing long-chain alkylamino group, organic modifier), 0.7 g; polyvinylpyrrolidone (dispersion aid), 0.04 g.
- vanadium dioxide nano powder and dispersion medium Disperse and disperse for 20 min at 1500 rad/min, and ultrasonically disperse for 60 min. Then add the dispersing aid and the aluminate coupling agent, and stir at a constant temperature of 80 °C on a high-speed mixer. 2 h, the precipitate was centrifuged again, and dried under vacuum at 60 ° C to obtain a vanadium dioxide nanopowder having a long-chain alkyl group attached thereto.
- each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 4 g; deionized water, 95.5 g; Modified polyurethane dispersant, 0.5 g.
- the organically modified nano-powder was added to deionized water for high-speed stirring and pre-dispersion for 5 min, then dispersing agent was added for ultrasonic dispersion for 60 min, and stirred on a high-speed mixer for 2 h. , a vanadium dioxide composite powder slurry is obtained.
- the main properties of the vanadium dioxide composite powder and its slurry obtained in this example are shown in Table 1.
- the mass percentage of each raw material is: polymer emulsion (polyurethane emulsion): 70%; this embodiment (2) Preparation of vanadium dioxide powder slurry (solid content 4%): 20%; deionized water: 8.5%; filming aid (propylene glycol monobutyl ether): 0.5%; wetting aid (polyethylene) Alcohol): 0.2%; Leveling agent (polyacrylate): 0.25%; defoamer (modified silicone compound): 0.25 %; thickener (cellulose thickener): 0.4%.
- the mass percentage of each raw material is: polymer emulsion (polyurethane emulsion): 40%; this embodiment (2) Preparation of vanadium dioxide powder slurry (solid content 4%): 30%; deionized water: 28%; filming aid (propylene glycol monobutyl ether): 0.5%; wetting aid (polyethylene) Alcohol): 0.2%; Leveling agent (polyacrylate): 0.25%; defoamer (modified silicone compound): 0.25 %; thickener (cellulose thickener): 0.4%; UV absorber (hydroxyphenyl s-triazine derivative): 0.5%.
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Comparative Example 6
- Waterborne titanate coupling agent Aqueous aluminate coupling agent Unmodified Surface group Polyvinyl alcohol Long chain alkylamino group Epoxy functional group Epoxy functional group Long chain alkylamino group - Dynamic light scattering particle size (nm) 20 ⁇ 100 50 ⁇ 300 20 ⁇ 150 50 ⁇ 150 50 ⁇ 200 20 ⁇ 200 BET specific surface area (m 3 /g) 60 ⁇ 70 45 ⁇ 55 50 ⁇ 60 50 ⁇ 60 45 ⁇ 55 40 ⁇ 50 Powder surface characteristics Hydrophilic Hydrophilic Hydrophilic Hydrophilic Hydrophilic Hydrophilic Hydrophilic Hydrophilic Hydrophilic 300 ° C weight loss 12% 4% 10% 8% 7% 1% Slurry storage for 3 months stability No precipitation Slight precipitation No precipitation No precipitation Slight precipitation Precipitation is more serious
- the coating of the present invention has a high visible light transmittance, and can almost completely shield ultraviolet rays, and can intelligently adjust the infrared rays with higher energy in sunlight (from high and low temperature infrared transmittance difference can be It can be seen that, at the same time, the coating has a transparent and bright appearance (low coating haze), aging resistance, water resistance, good adhesion and strong scrub resistance; and compared with the non-organic modified VO 2 slurry (Comparative Example 6), The coating obtained by the method has better intelligent regulation rate, low visible light transmittance and less haze.
- the vanadium dioxide composite powder of the invention can be applied to the preparation of intelligent energy-saving coatings or coatings, and the prepared coating has high transparency, low haze and strong aging resistance, and is mainly applied to flexible materials such as films and braids. It can also be used for heat insulation applications such as glass and exterior walls. It can also be widely used in energy saving and emission reduction equipment, such as energy-saving thin films, energy-saving coatings, solar temperature control devices, or energy information equipment, such as miniature photoelectric switching devices, thermistors, battery materials, and optical information storage devices.
- the preparation method of the vanadium dioxide composite powder provided by the invention, the preparation process innovation, the vanadium dioxide (vanadium dioxide) and the doped nano powder thereof can be effectively improved by the organic surface modification process of the organic modifier Dispersibility and chemical stability.
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Abstract
Description
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例6 | |
改性剂 | 含水溶性长链的硅烷偶联剂 | 含水溶性长链的硅烷偶联剂 | 含水溶性长链的硅烷偶联剂 | 水性钛酸酯偶联剂 | 水性铝酸酯偶联剂 | 未改性 |
表面基团 | 聚乙烯醇 | 长链烷基胺基基团 | 环氧官能化基团 | 环氧官能化基团 | 长链烷基胺基基团 | - |
动态光散射粒径(nm) | 20~100 | 50~300 | 20~150 | 50~150 | 50~200 | 20~200 |
BET比表面积(m3/g) | 60~70 | 45~55 | 50~60 | 50~60 | 45~55 | 40~50 |
粉体表面特性 | 亲水 | 亲水 | 亲水 | 亲水 | 亲水 | 亲水 |
300℃失重 | 12% | 4% | 10% | 8% | 7% | 1% |
浆料存放3个月稳定性 | 不沉淀 | 轻微沉淀 | 不沉淀 | 不沉淀 | 轻微沉淀 | 沉淀较为严重 |
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例6 | ||
基体树脂 | 聚氨酯乳液 | 聚氨酯乳液 | 丙烯酸乳液 | 丙烯酸乳液 | 聚氨酯乳液 | 聚氨酯乳液 | |
VO2粒子 | 有机改性 | 有机改性 | 有机改性 | 有机改性 | 有机改性 | 未改性 | |
涂布方式 | 辊涂 | 辊涂 | 喷涂 | 辊涂 | 刮涂 | 刮涂 | |
涂层厚度 | 3.5um | 4.5um | 6.5um | 2.5um | 5.5um | 5.5um | |
可见光透过率 | 53% | 38% | 55% | 65% | 45% | 30% | |
红外线透过率 | 高温 | 37.1% | 30% | 43.5% | 35% | 38% | 35% |
低温 | 61.3% | 47% | 70% | 55% | 58% | 45% | |
红外调节率 | 24.2% | 17% | 26.5% | 20% | 20% | 10% | |
1500nm高低温差值 | 36.8% | 23% | 35.6% | 30% | 28% | 19% | |
紫外线阻隔率 | 99% | 99% | 99% | 97% | 90% | 92% | |
耐水性 | 96h无异常 | 96h无异常 | 96h无异常 | 96h无异常 | 96h无异常 | 96h无异常 | |
耐人工气候老化性 | 1000h 无剥落,不起泡,无裂痕 | 1000h 无剥落,不起泡,无裂痕 | 1000h 无剥落,不起泡,无裂痕 | 1000h 无剥落,不起泡,无裂痕 | 600h 无剥落,不起泡,无裂痕 | 1000h 无剥落,不起泡,无裂痕 | |
耐刷洗性/次 | 5000 | 5000 | 7000 | 7000 | 5000 | 5000 | |
涂层雾度 | <5% | <15% | <10% | <5% | <8% | >15% | |
涂层耐温变性 | 无异常 | 无异常 | 无异常 | 无异常 | 无异常 | 无异常 |
Claims (23)
- 一种二氧化钒智能温控涂层 ,其特征在于, 所述涂层由二氧化钒粉体浆料、聚合物乳液和涂料助剂混合后涂布在基材而形成;且所述二氧化钒粉体浆料包括二氧化钒复合粉体和分散介质 ,所述二氧化钒复合粉体包括化学组成为 V1-xMxO2 的二氧化钒纳米粉体,且所述纳米粉体表面接有机改性长链分子 ,其中 M 为掺杂元素, 0 ≤ x ≤ 0.5 。
- 根据权利要求 1 所述的二氧化钒智能温控涂层,其特征在于,所述有机改性长链分子含量在 0.1 ~ 50% 。
- 根据权利要求 2 所述的二氧化钒智能温控涂层,其特征在于,所述有机改性长链分子含量在 1 ~ 10% 。
- 根据权利要求 1 所述的二氧化钒智能温控涂层,其特征在于,所述有机改性长链分子链长度在 0.1nm ~ 100nm 。
- 根据权利要求 1 - 4 中任一项所述的二氧化钒智能温控涂层,其特征在于,所述有机改性长链分子为官能化有机长链。
- 根据权利要求 1 - 4 中任一项所述的二氧化钒智能温控涂层,其特征在于,所述官能化有机长链是长链烷基、聚丙烯酸基团、聚乙烯醇基团、环氧基团、长链烷基胺基团、卤化长链烷基、和 / 或羧基化长链烷基。
- 根据权利要求 1 ~ 4 中任一项所述的二氧化钒智能温控涂层,其特征在于,所述粉体为金红石相二氧化钒纳米粉体,相变温度在 -20 ~ 70 ℃可调。
- 根据权利要求 7 所述的二氧化钒智能温控涂层,其特征在于,所述掺杂元素 M 是元素周期表中钒附近的 21 ~ 30 过渡元素、锡及其附近的元素和钨、钼、钌、铌中的一个或者任意组合。
- 根据权利要求 8 所述的二氧化钒智能温控涂层,其特征在于,元素周期表中钒附近的 21 ~ 30 过渡元素包括钪、钛、铬、锰、铁、钴、镍、铜、和锌,所述锡及其附近的元素包括铟、锑、锡、镓、锗、铅、和铋。
- 根据权利要求 1 ~ 4 中任一项所述的二氧化钒智能温控涂层,其特征在于,所述二氧化钒复合粉体的颗粒尺寸在 200nm 以下。
- 根据权利要求 1 ~ 4 中任一项所述的二氧化钒智能温控涂层 ,其特征在于, 所述涂层中二氧化钒复合粉体的固含量为 0.1%-50% 。
- 根据权利要求 11 所述的二氧化钒智能温控涂层 ,其特征在于, 所述涂层中二氧化钒复合粉体的固含量为 2 %-20 % 。
- 根据权利要求 1 ~ 4 中任一项所述的二氧化钒智能温控涂层 ,其特征在于,所述涂层干膜厚度为 0.05~50 u m 。
- 根据权利要求 1 ~ 4 中任一项所述的二氧化钒智能温控涂层 ,其特征在于,所述聚合物乳液为高分子树脂的水分散体或者乳液,是聚丙烯酸树脂、聚酯树脂、聚氨酯树脂、有机硅树脂、醇酸树脂和环氧树脂中的一种或几种。
- 根据权利要求 1 ~ 4 中任一项所述的二氧化钒智能温控涂层 ,其特征在于,所述涂料助剂包括成膜助剂、润湿剂、消泡剂、增稠剂和流平剂。
- 根据权利要求 15 所述的二氧化钒智能温控涂层 ,其特征在于,所述成膜助剂为乙二醇单丁醚、丙二醇单丁醚、二丙二醇甲醚乙醚酯、丙二醇单丁醚、乙二醇丙醚、二丙醚中的一种或几种。
- 根据权利要求 15 所述的二氧化钒智能温控涂层 ,其特征在于,所述润湿助剂为十二烷基硫酸盐、十二烷基磺酸盐、聚乙烯醇、聚乙烯吡咯烷酮、有机硅化合物和有机氟化合物中的一种或几种。
- 根据权利要求 15 所述的二氧化钒智能温控涂层 ,其特征在于,所述消泡剂为二甲基硅油、醚酯化合物、改性矿物油、聚氧乙基甘油醚、小分子金属有机物和改性有机硅聚合物中的一种或几种。
- 根据权利要求 15 所述的二氧化钒智能温控涂层 ,其特征在于,所述流平剂为乙二醇丁醚、醋丁纤维素、聚丙烯酸酯类、硅油和改性有机硅化合物中的一种或几种。
- 根据权利要求 15 所述的二氧化钒智能温控涂层 ,其特征在于,所述增稠剂为纤维素类增稠剂,聚乙烯蜡、气相二氧化硅、聚丙烯酸类增稠剂,或缔合型聚氨酯类增稠剂。
- 根据权利要求 1 所述的二氧化钒智能温控涂层 ,其特征在于,在形成所述涂层的混合液中还包括紫外线吸收剂,所述紫外线吸收剂为二苯甲酮及其衍生物、邻羟基苯基苯并三唑及其衍生物、芳香酯类化合物或羟基苯基均三嗪及其衍生物。
- 根据权利要求 1 所述的二氧化钒智能温控涂层 ,其特征在于,所述基材是 PP 、 PE 、 PA 、 PVC 、 PET 或 PMMA 的塑料薄膜,或者由所述材料制备的纤维或编织袋。
- 根据权利要求 1 所述的二氧化钒智能温控涂层 ,其特征在于,所述涂布方式包括喷涂、刮涂、刷涂、淋涂或辊涂的涂布方式。
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JP2014552474A JP2015513508A (ja) | 2012-01-19 | 2012-03-07 | 二酸化バナジウムの複合粉体、二酸化バナジウム粉体スラリー、二酸化バナジウムのスマート温度制御コーティング層の製造方法 |
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JP (1) | JP2015513508A (zh) |
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US9650520B2 (en) | 2017-05-16 |
CN103073943B (zh) | 2014-09-17 |
US20150132494A1 (en) | 2015-05-14 |
CN103073943A (zh) | 2013-05-01 |
JP2015513508A (ja) | 2015-05-14 |
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