CN106978005A

CN106978005A - A kind of tungstenic metal oxide nanoparticles and preparation method thereof

Info

Publication number: CN106978005A
Application number: CN201710125217.9A
Authority: CN
Inventors: 张纪尧; 钟杰; 李海霞; 杨程
Original assignee: Singapore Nano-Material Science & Technology Co Ltd; XIAMEN NANUO TAIKE TECHNOLOGY Co Ltd
Current assignee: Singapore Nano-Material Science & Technology Co Ltd; XIAMEN NANUO TAIKE TECHNOLOGY Co Ltd
Priority date: 2017-03-03
Filing date: 2017-03-03
Publication date: 2017-07-25

Abstract

The present invention provides a kind of tungstenic metal oxide nanoparticles and preparation method thereof, and the preparation method comprises the following steps：The predecessor of tungsten oxide and the predecessor of doping metals are provided, wherein one or more of the doping metals in IA~VA races metal, transition metal；The predecessor of the tungsten oxide, the predecessor of doping metals and reducing agent, solvent are mixed to form reaction slurry, tungstenic metal oxide nanoparticles are generated after reduction reaction.The preparation method is completed using a step wet method, and preparation method is easy to operate and large-scale production, and compared with existing calcination method or precipitation aging two-step method, granularity evenly, and is easier to be scattered in medium, forms the dispersion of transparent and homogeneous.Meanwhile, this preparation method has more cost advantage.

Description

A kind of tungstenic metal oxide nanoparticles and preparation method thereof

Technical field

The present invention relates to heat-barrier material technical field, specifically, be related to a kind of tungstenic metal oxide nanoparticles and Its preparation method.

Background technology

Modern architecture is more and more using glass to improve the effect of landscape and visual aspects, while glass is used as vehicle window Also widely apply on automobile, train.On the one hand glass improve the experience of user, but then, due to sunshine Irradiation, but makes incoming indoor, in-car heat increase, temperature rise, particularly in summer, can dramatically increase air conditioning electricity consumption and Energy resource consumption.Begin to use thermal isolation film on energy consumption, increasing glass of building and glass for vehicle window to reduce.

The wavelength band for the solar radiation observed on the ground is 295~2500nm, reaches the sun light direct beam on ground Energy density is about 930W/m².In the Energy distribution of solar spectrum, ultraviolet spectra area (300~380nm) is about 3%, it is seen that Spectral regions (380~780nm) are about 44%, and infrared spectral region (780~2500nm) is about 53%.As can be seen here, it is invisible Light, including infrared ray (being located at infrared spectral region) and ultraviolet (being located at ultraviolet spectra area), carry most sunshine straight Penetrate energy.Therefore, preferable solar insulation film is transparent to visible ray, meanwhile, it is capable to hinder sunshine every ultraviolet spectra Energy entrained by area and infrared spectral region.

At present, has there are a variety of thermal isolation film products in the market, wherein the heat-barrier material used mainly has tin-antiomony oxide (ATO), zinc oxide aluminum (AZO), tin indium oxide (ITO), lanthanum hexaboride (LaB₆), caesium tungsten bronze (Cs_0.3WO₃) etc. compound.

Wherein, caesium tungsten bronze is that to report in recent years have the compound of good barrier effect, but mesh to infrared spectral region The preparation technology of preceding caesium tungsten bronze powder is complicated, and cost is higher.It is calcination method than more typical preparation method, i.e. press raw material Certain proportion is mixed, and in reducing atmosphere environment and under hot conditions, raw material is calcined, made annealing treatment.The technique is obtained Product particle easily reunite after calcining, particle size is larger and is difficult to disperse, it is impossible to be directly used in manufacture sunshine Barrier articles, such as sun thermal isolation film or coating.

The content of the invention

The problem of existing for prior art, the present invention provides a kind of preparation side of tungstenic metal oxide nanoparticles Method, the preparation method comprises the following steps：

The predecessor of tungsten oxide and the predecessor of doping metals are provided, wherein the doping metals are selected from IA~VA races gold One or more in category, transition metal；

The predecessor of the tungsten oxide, the predecessor of doping metals and reducing agent, solvent are mixed to form reaction slurry, passed through Tungstenic metal oxide nanoparticles are generated after reduction reaction.

Preferably, the mass ratio of the predecessor of the tungsten oxide, the predecessor of doping metals and reducing agent is 10：1~10： 1~50.

Preferably, the temperature of the reduction reaction is 250~350 DEG C.

Preferably, the predecessor of the tungsten oxide is selected from ammonium metatungstate, positive ammonium tungstate, ammonium paratungstate, wolframic acid, silication Tungsten, tungsten sulfide, chlorine oxygen tungsten, tungsten hexachloride, tungsten tetrachloride, tungsten bromide, tungsten fluoride, tungsten carbide, oxidation of coal tungsten or aforementioned substances Combination.

Preferably, the predecessor of the doping metals be selected from the hydroxide of IA~VA races metal, halide, carbonate, Sulfate, nitrate, formates, acetate, hydroxide, halide, carbonate, the sulfuric acid of citrate and transition metal Salt, nitrate, formates, acetate, the combination of citrate or aforementioned substances.

Preferably, the reducing agent is selected from the combination of hydrazine hydrate, citric acid, winter propylhomoserin, ASP or aforementioned substances.

Preferably, the solvent is selected from the combination of water, methanol, ethanol, isopropanol, butanol or aforementioned substances.

The present invention also provides a kind of tungstenic metal oxide nanoparticles, and the tungstenic metal oxide nanoparticles are by upper The preparation method stated is made.

Preferably, shown in the tungstenic metal oxide nanoparticles such as formula (1)：

N_xM_yWO_zFormula (1),

Wherein, N, M are doping metals and the one or more in IA~VA races metal, transition metal, and W is tungsten, and O is Oxygen, 0≤x≤1,0<Y≤1,2<z<3.5.

Preferably, the average grain diameter of the tungstenic metal oxide nanoparticles is 10~100nm.

Compared with prior art, the present invention at least has the advantages that：

The preparation method of the tungstenic metal oxide nanoparticles of the present invention is completed using a step wet method, and preparation method is easily grasped Make and large-scale production, compared with existing calcination method or precipitation-aging two-step method, granularity evenly, and is easier to be scattered in In medium, the dispersion of transparent and homogeneous is formed.This preparation method has more cost advantage, meanwhile, obtained undried tungstenic The filter cake of metal oxide nanoparticles is used directly for preparing tungstenic metal oxide nanoparticles dispersion, can avoid Dry tungstenic metal oxide nanoparticles occur to reunite and the average grain diameter as caused by twice dispersing becomes big risk.

Brief description of the drawings

Fig. 1 is the flow chart of the preparation method of the tungstenic metal oxide nanoparticles of the embodiment of the present invention；

Fig. 2 is the flow chart of the preparation method of the tungstenic metal oxide nanoparticles dispersion of the embodiment of the present invention；

Fig. 3 is the schematic cross-section of the solar insulation film of one embodiment of the invention；

Fig. 4 is the schematic cross-section of the solar insulation film of another embodiment of the present invention；

The schematic diagram of the solar insulation film application that Fig. 5 is Fig. 3 on the glass substrate；

Fig. 6 is the schematic cross-section of the solar insulation glass of one embodiment of the invention；

Fig. 7 schemes for the SEM of the tungstenic metal oxide nanoparticles of the embodiment of the present invention 1；

Fig. 8 is the XRD of the tungstenic metal oxide nanoparticles of the embodiment of the present invention 1；

Fig. 9 is the EDX analysis results of the tungstenic metal oxide nanoparticles of the embodiment of the present invention 1；

Figure 10 schemes for the XPS of the tungstenic metal oxide nanoparticles of the embodiment of the present invention 1；

Figure 11 schemes for the SEM of the tungstenic metal oxide nanoparticles of the embodiment of the present invention 4；

Figure 12 is the EDX analysis results of the tungstenic metal oxide nanoparticles of the embodiment of the present invention 4；

Figure 13 schemes for the XPS of the tungstenic metal oxide nanoparticles of the embodiment of the present invention 4；

Figure 14 is the grading curve of the tungstenic metal oxide nanoparticles dispersion of the embodiment of the present invention 6；

Figure 15 is the grading curve of the tungstenic metal oxide nanoparticles dispersion of the embodiment of the present invention 7；

Figure 16 is the grading curve of the tungstenic metal oxide nanoparticles dispersion of the embodiment of the present invention 8；

Figure 17 is the grading curve of the tungstenic metal oxide nanoparticles dispersion of the embodiment of the present invention 9；

Figure 18 is the grading curve of the tungstenic metal oxide nanoparticles dispersion of the embodiment of the present invention 10；

Figure 19 is the light transmission rate curve of the solar insulation film of the embodiment of the present invention 13 at different wavelengths；

Figure 20 is the light transmission rate curve of the solar insulation film of the embodiment of the present invention 14 at different wavelengths；

Figure 21 is the light transmission rate curve of the solar insulation film of the embodiment of the present invention 15 at different wavelengths；

Figure 22 is the light transmission rate curve of the solar insulation film of the embodiment of the present invention 16 at different wavelengths；

Figure 23 is the light transmission rate curve of the solar insulation glass of the embodiment of the present invention 17 at different wavelengths；

Figure 24 is the light transmission rate curve of the solar insulation glass of the embodiment of the present invention 18 at different wavelengths.

Embodiment

Example embodiment is described more fully with referring now to accompanying drawing.However, example embodiment can be with a variety of shapes Formula is implemented, and is not understood as limited to embodiment set forth herein；On the contrary, thesing embodiments are provided so that the present invention more Fully and completely, and by the design of example embodiment those skilled in the art is comprehensively conveyed to.

One aspect of the present invention provides a kind of preparation method of tungstenic metal oxide nanoparticles, and this contains tungsten metal oxidic Nano particle is used to manufacture solar insulation film.

Fig. 1 is refer to, the preparation method comprises the following steps：

Step S101：The predecessor of tungsten oxide and the predecessor of doping metals are provided, wherein doping metals are selected from IA~VA One or more in race's metal, transition metal.

In one embodiment, the predecessor of tungsten oxide includes but is not limited to be ammonium metatungstate, positive ammonium tungstate, para-tungstic acid Ammonium, wolframic acid, tungsten silicide, tungsten sulfide, chlorine oxygen tungsten, tungsten hexachloride, tungsten tetrachloride, tungsten bromide, tungsten fluoride, tungsten carbide, oxidation of coal tungsten, Aforementioned substances can also be applied in combination, preferably ammonium metatungstate, positive ammonium tungstate, ammonium paratungstate, wolframic acid.

In one embodiment, doping metals include but is not limited to be IA~VA races metal, the lithium in transition metal, sodium, Potassium, rubidium, caesium, aluminium, indium, gallium, tin, manganese, iron, cobalt, nickel, copper, zinc, antimony, chromium, molybdenum, cadmium.The predecessor of doping metals can be selected from IA Hydroxide, halide, carbonate, sulfate, nitrate, formates, acetate, citrate and the mistake of~VA races metal Cross hydroxide, halide, carbonate, sulfate, nitrate, formates, acetate, citrate or the aforementioned substances of metal Combination.As an example, such as cesium hydroxide, cesium carbonate, citric acid caesium, stannic chloride, tin oxide, stannic hydroxide.

Step S102：The predecessor of tungsten oxide, the predecessor of doping metals and reducing agent, solvent are mixed to form reaction material Slurry, generates tungstenic metal oxide nanoparticles after reduction reaction.

In step S102, reducing agent can use organic reducing agent and/or inorganic reducing agent, can also use hydrogen, mix Miscellaneous metal simple-substance etc., preferably organic reducing agent and/or inorganic reducing agent.As an example, organic reducing agent include but is not limited to be The reducing agents such as alcohols, organic acid, amino acids, carbohydrate, amine, such as hydrazine hydrate, citric acid, winter propylhomoserin, ASP；It is inorganic Reducing agent includes but is not limited to be metallic boron hydrides, hydride, such as sodium borohydride, potassium borohydride, sodium hydride, hydrofining, hydrogen Change calcium.

In step S102, solvent can use water, alcohols, ketone, ethers, esters, aldehydes, amine, arene, alkane Class etc. is from polarity to nonpolar all kinds of solvents, and aforementioned solvents can be used in mixed way as needed, in a preferred embodiment, solvent Combination selected from water, methanol, ethanol, isopropanol, butanol or aforementioned solvents.Wherein, alcohols solvent has reproducibility, anti-in high temperature During answering, the effect of assisted Reduction can be played.In addition, during the course of the reaction, having the Ester generation for being insoluble in water, instead The presence for having alcohols in medium is answered, after the reaction during separation of solid and liquid, it is easier to purify particle, reduce pollution.

In step S102, the mass ratio of the predecessor of tungsten oxide, the predecessor of doping metals and reducing agent is：10：1~ 10：1~50.The solids content for the mixture being made up of the predecessor of tungsten oxide, the predecessor of doping metals, reducing agent and solvent For 1~50wt%.

In one embodiment, the temperature of reduction reaction is 100~400 DEG C in step S102.In this 100~400 DEG C of temperature Under degree, reduction reaction can be completed by 1~24h stirring, the slurry of tungstenic metal oxide nanoparticles is obtained.At one In embodiment, after reduction reaction, weight ratio (wt%) of the tungstenic metal oxide nanoparticles in reaction slurry be 0.1%~ 50%.In a preferred embodiment, the temperature of reduction reaction is 250~350 DEG C in step S102, complete by 3~24h stirring Into after reduction reaction, weight ratio (wt%) of the tungstenic metal oxide nanoparticles in reaction slurry is 2%~20%.

In one embodiment, in the preparation method of tungstenic metal oxide nanoparticles of the invention, in addition to containing The step S103 that tungsten metal oxidic nano particle is separated.Specifically, after reduction reaction, to including tungstenic metal oxygen The reaction slurry of compound nano particle carries out separation of solid and liquid and obtains crude product, and the method for separation of solid and liquid can use centrifugal method, Filter method, such as plate-frame filtering can be used.

Further, above-mentioned preparation method also includes, and includes the crude product of tungstenic metal oxide nanoparticles to what is obtained The step S104 purified.Specifically, crude product will be obtained it is dispersed in decentralized medium to be washed, then carries out solid-liquid point From, and repeat above-mentioned purge process, it is generally pure up to the purity for obtaining tungstenic metal oxide nanoparticles reaches requirement The number of times of change is 2~5 times, obtains the filter cake of tungstenic metal oxide nanoparticles.

In step S104, decentralized medium can selected from water, alcohols, ketone, ethers, esters, aldehydes, amine, arene, Alkanes etc. are from polarity to nonpolar all kinds of solvents, and aforementioned solvents can be used in mixed way as needed.

Further, above-mentioned preparation method also includes, and the filter cake of tungstenic metal oxide nanoparticles after purification is entered The step S105 that row is dried, smashed, obtains powder.

The preparation method of above-mentioned tungstenic metal oxide nanoparticles using a step wet method complete, preparation method it is easy to operate and Large-scale production, compared with existing calcination method or precipitation-aging two-step method, with more cost advantage, meanwhile, above-mentioned steps The filter cake of isolated undried tungstenic metal oxide nanoparticles is used directly for preparing tungstenic metal in S104 Oxide nano particles dispersion, without being dried and crushing to it, can avoid drying contains tungsten metal oxidic Nano particle occurs to reunite and the average grain diameter as caused by twice dispersing becomes big risk.

Another aspect of the present invention also provides a kind of tungstenic metal oxide nanoparticles, the tungstenic metal oxide nano Grain is made by above-mentioned preparation method.

In a preferred embodiment, shown in the tungstenic metal oxide nanoparticles such as formula (1)：

N_xM_yWO_zFormula (1),

In a preferred embodiment, the tungstenic metal oxide nanoparticles are made by above-mentioned preparation method.Obtain tungstenic The average grain diameter of metal oxide nanoparticles is 5~1000nm, it is preferable that its average grain diameter is 10~100nm.

The tungstenic metal oxide nanoparticles as made from above-mentioned preparation method have average grain diameter small, uniform particle sizes excellent Point.There is obtained tungstenic metal oxide nanoparticles high visible to pass through and sunshine infrared spectral region can be selected Selecting property absorbs the characteristic of barrier, is used as making solar insulation coating and the ideal material of thermal isolation film.

Another aspect of the present invention also provides a kind of preparation method of tungstenic metal oxide nanoparticles dispersion, refer to Fig. 2, the preparation method comprises the following steps：

Step S201：A slurry is provided, slurry includes solvent and the tungstenic metal oxide nano being dispersed in the solvent Particle.

In the preparation method of the dispersion of the present invention, tungstenic metal oxide nanoparticles can be not only used such as formula (1) Shown tungstenic metal oxide nanoparticles, the tungstenic metal oxide nanoparticles that other can also be used to constitute.

In a preferred embodiment, the tungstenic metal oxide nanoparticles used in step S201 are by above-mentioned tungstenic gold The tungstenic metal oxide nanoparticles that the preparation method of category oxide nano particles is made.In an alternative embodiment, this contains Tungsten metal oxidic nano particle can also use commercially available tungstenic metal oxide nanoparticles, such as commercially available caesium tungsten bronze (Cs_0.3WO₃) nano particle.

In a preferred embodiment, in step S201, slurry will be by that will include solvent and tungstenic metal oxide nano The filter cake of grain is scattered to be formed in a solvent, therefore, can be directly using tungstenic metal oxide nanoparticles in step S201 The filter cake of isolated tungstenic metal oxide nanoparticles in the step S104 of preparation method, without being done to it It is dry and crush, as caused by twice dispersing average grain diameter can be avoided to become big risk, the dispersion of preparation is transparent and translucency It is high.

In step S201, solvent can use water, alcohols, ketone, ethers, esters, aldehydes, amine, arene, alkane Class etc. is from polarity to nonpolar all kinds of solvents, and aforementioned solvents can be used in mixed way as needed, in a preferred embodiment, solvent For alcohols solvent, more specifically, the alcohols solvent is selected from methanol, ethanol, propyl alcohol or its combination.

In step S201, tungstenic metal oxide nanoparticles it is scattered in a solvent after, its weight ratio in slurry is 0.1%~50%, it is preferable that its weight ratio in slurry is 5%~20%, nano particle is can be uniformly dispersed in medium In, while making slurry keep good mobility.

Step S202：Surface modifier is added into slurry and is reacted to reaction and is terminated.

In step S202, surface modifier is selected from coupling agent, surfactant, organosilicon, unsaturated organic acid and organic Oligomer, high score subclass stabilizer, phosphate, the combination of organic amine or aforementioned substances, specifically, surface modifier include but It is not limited to silane coupler.

In a preferred embodiment, surface modifier is added in slurry afterwards in a solvent by dissolving, used in dissolving Solvent is preferably identical with the solvent in step S201.

In one embodiment, the mass ratio of the surface modifier added in slurry and tungstenic metal oxide nanoparticles For 0.05~0.15：1, to ensure there are enough surface modifiers, nano grain surface is fully modified modification.

In one embodiment, the temperature reacted in step S202 be 20~100 DEG C, the temperature preferably reacted be 60~ 100 DEG C, improve modifying agent hydrolysis rate.The time of reaction can be 10min~24h, and the typical reaction time is 5~10h, is made Surfactant can fully react with particle surface.

, can be to tungstenic gold by adding surface modifier into slurry and being reacted with tungstenic metal oxide nanoparticles The surface of category oxide nano particles is modified.Such as：By taking silane coupler as an example, due to tungstenic metal oxide nanoparticles There are a large amount of-OH on surface, and silane coupler forms silanol (HO-Si-R) after hydrolyzing, and the hydroxyl-OH of silanol and particle surface enters Single step reaction, dehydration, particle surface (X represents particle) is acted on X-O-Si-R, by selecting different functional groups, change Grain surface polarity, so as to be scattered in the solvent of opposed polarity.Specifically, when the solvent for forming dispersion is water, alcohol During the larger solvent of class isopolarity, the surface modifiers such as amine, KH560 can be used to tungstenic metal oxide nanoparticles table Face is modified, and its surface is had hydrophilic radical；It is ethers, esters, arene, alkanes etc. when forming the solvent of dispersion In the less solvent of polarity, long chain silane coupling agent can be used, such as：The surfaces such as cetyl trimethyl silane coupler are modified Agent is modified to tungstenic metal oxide nanoparticles surface, its surface is had lipophilic group.

Step S203：Tungstenic metal oxide nanoparticles after surface treated in slurry are separated.

In step S203, the method for separation is preferred to use centrifugation, filtering or heating evaporation method for concentration, wherein, filtering side Method can use plate-frame filtering.Further, step S203 is also including the tungstenic metal oxygen after the surface treated to separating Compound nano particle is dried.

Step S204：Tungstenic metal oxide nanoparticles are dispersed in the solvent of setting again, tungstenic metal is obtained Oxide nano particles dispersion.

The preparation method of above-mentioned tungstenic metal oxide nanoparticles dispersion makes to contain by wet process surface treatment and modification Surface modifier of the tungsten metal oxidic particles surface covered with different functional groups, so as to finally be dispersed among water, alcohols, ketone Class, ethers, esters, aldehydes, amine, arene, alkanes etc. form transparent point from polarity to nonpolar all kinds of solvents Granular media.

With existing since dry powder, compared using the method for physical grinding legal system back-up granular media, the present invention uses wet method Nano particle need not be dried for the method that surface treatment forms dispersion, and directly particle surface is repaiied in the liquid phase Decorations, so as to avoid the hard aggregation of particle, operating method is simple and easy to apply, be easy to industrialized production；Meanwhile, pass through the side of the present invention The dispersion solid content of method formation is high, and decentralization is high, aggregate particle size narrowly distributing, and average aggregate particle size is 30~100nm.

Another aspect of the present invention also provides a kind of tungstenic metal oxide nanoparticles dispersion, and this contains tungsten metal oxidic Nanoparticle dispersion is formed by the preparation method of above-mentioned dispersion.

In a preferred embodiment, in above-mentioned dispersion, shown in tungstenic metal oxide nanoparticles such as formula (1)：

N_xM_yWO_zFormula (1),

In one embodiment, in the dispersion of formation, the weight ratios of tungstenic metal oxide nanoparticles for 0.1%~ 70%, preferably 30%~50%, the dispersion has higher solid content.

In one embodiment, in the dispersion of formation, the average grain diameters of tungstenic metal oxide nanoparticles for 1~ 200nm, preferably 30~100nm, have the advantages that aggregate particle size narrowly distributing, average aggregate particle size are small.

Further aspect of the present invention provides a kind of solar insulation coating, the solar insulation coating be used to preparing sunshine every Hotting mask has the advantages that high transparency and high heat-insulated rate, and the most infrared light and ultraviolet light that can be absorbed in barrier sunshine are taken The energy of band.

Specifically, the solar insulation coating includes following components：Nano inorganic infrared ray absorbing barrier agent dispersion, Nano inorganic ultraviolet radiation absorption barrier agent dispersion, organic uv absorbers, resin and solvent diluent.

By weight percentage, the content of each component is in above-mentioned solar insulation coating：Nano inorganic infrared ray absorbing Obstruct agent dispersion, 5~70%；Nano inorganic ultraviolet radiation absorption obstructs agent dispersion, 1~20%；Organic uv absorbers, 0~10%；Resin, 20~80%；Solvent diluent, 0~50%.Using the specific proportioning and the solar insulation coating of composition The solar insulation film of preparation can absorb the energy that the most black light in barrier sunshine is carried, simultaneously, it is seen that The transmitance of light is high, reflects small.

Wherein, the nano inorganic infrared ray absorbing barrier in nano inorganic infrared ray absorbing barrier agent dispersion is used to hinder , can be using the known material with good infrared light barrier property every the energy entrained by the infrared spectral region of sunshine. In a preferred embodiment, the infrared ray absorbing barrier in nano inorganic infrared ray absorbing barrier agent dispersion is tungstenic metal Oxide nano particles, tungstenic metal oxide nanoparticles due to the characteristic of its plasma, can selective resistance every the sun Energy entrained by light middle infrared spectral region, but the transmission of visible ray is not influenceed.The present invention is not limited for disperseing tungstenic metal The type of the decentralized medium of oxide nano particles, the decentralized medium can selected from water, alcohols, ketone, ethers, esters, aldehydes, Benzene class, alkanes etc. are from polarity to nonpolar all kinds of solvents, and aforementioned solvents can be used alone, can also be applied in combination.

In a preferred embodiment, tungsten metal oxidic nanoparticle dispersion is by including step S201~step S204 preparation method is made.In an alternative embodiment, tungstenic metal oxide nanoparticles dispersion can also use city The dispersion sold.

In one embodiment, in tungstenic metal oxide nanoparticles dispersion, tungstenic metal oxide nanoparticles Mass content be 1%~50%.In one embodiment, an average grain diameter of tungstenic metal oxide nanoparticles is 5 ~1000nm, it is preferable that its average grain diameter is 10~100nm, it is highly preferred that its average grain diameter is 10~50nm. In a preferred embodiment, in nano inorganic infrared ray absorbing barrier agent dispersion, the two of tungstenic metal oxide nanoparticles Secondary average grain diameter is 30~100nm.

Further, shown in the tungstenic metal oxide nanoparticles such as formula (1)：

N_xM_yWO_zFormula (1),

Wherein, N, M are doping metals and the one or more in IA~VA races metal, transition metal, and W is tungsten, and O is Oxygen, 0≤x≤1,0<Y≤1,2<z<3.5.In one embodiment, doping metals N, M includes but is not limited to be IA~VA races gold Category, the lithium in transition metal, sodium, potassium, rubidium, caesium, aluminium, indium, gallium, tin, manganese, iron, cobalt, nickel, copper, zinc, antimony, chromium, molybdenum, cadmium.One In individual specific embodiment, the tungstenic metal oxide nanoparticles are caesium tungsten bronze (Cs_0.3WO₃) nano particle.

Nano inorganic ultraviolet radiation absorption barrier in nano inorganic ultraviolet radiation absorption barrier agent dispersion is used to obstruct too Energy entrained by the ultraviolet spectra area of sunlight, in a preferred embodiment, the nano inorganic ultraviolet radiation absorption barrier are selected from Nano zine oxide (ZnO), nano-cerium oxide (CeO₂) and mix at least one of zinc aluminum oxide (AZO).Nano zine oxide, nanometer Cerium oxide and mix zinc aluminum oxide due to the characteristic of its plasma, can selective resistance every entrained by ultraviolet spectra area in sunshine Energy, formed plasma resonance, so as to absorb ultraviolet light but not influence the transmission of visible ray.

Further, nano zine oxide, nano-cerium oxide and mix zinc aluminum oxide and can be scattered in water, alcohols, ketone, ether Dispersion is formed in class, esters, aldehydes, benzene class, alkanes equal solvent, aforementioned solvents can be used alone, can also be applied in combination, The mass content of nano inorganic ultraviolet radiation absorption barrier can be in the nano inorganic UV absorption barrier agent dispersion of formation In the range of 1%~50%.

In nano inorganic ultraviolet radiation absorption barrier agent dispersion, the grain that is once averaged of nano inorganic ultraviolet radiation absorption barrier Footpath can be 10~30nm, and the quadratic average particle diameter of the nano inorganic ultraviolet radiation absorption barrier can be 30~70nm.

The solar insulation coating of the present invention also includes organic uv absorbers, and the organic uv absorbers may be selected from Salicylate ultraviolet absorbent, benzophenone class ultra-violet absorber, Benzotriazole Ultraviolet Stabilizer, group-substituted acrylonitrile At least one of ultra-violet absorber, triazine-based ultraviolet absorbent, hindered amines ultra-violet absorber.Due to nano inorganic Ultraviolet radiation absorption barrier may be not enough to the uv absorption capacity of a small amount of range of wavelengths, by increasing organic ultraviolet line absorption Agent, can make up inorganic UV line absorption barrier defect that may be present, further enhance the ultraviolet of solar insulation coating Line absorption ability.

Resin adhesive is a continuous phase structure as carrier, above-mentioned nano inorganic infrared ray absorbing barrier and is received Rice inorganic UV line absorption barrier can be uniformly distributed in resin adhesive, and uniformly continuous is formed together with resin adhesive Composite construction, the resinoid bond has stronger adhesiveness, and glass base can be preferably attached at when being prepared into thermal isolation film On material.In a preferred embodiment, the resin is selected from least one of polyacrylic resin, organic siliconresin, polyurethane.

When preparing solar insulation coating, solvent diluent is used to obstruct mixed nano inorganic infrared ray absorbing Agent dispersion, nano inorganic ultraviolet radiation absorption barrier agent dispersion, organic uv absorbers and resin are diluted, make its into For uniform mixed phase.In one embodiment, solvent diluent can selected from water, alcohols, ketone, ethers, esters, aldehydes, At least one of benzene class, alkane solvents.

Fig. 3 is refer to, another aspect of the present invention provides a kind of solar insulation film 20, and the solar insulation film 20 includes one Complex functional layer 22, the complex functional layer 22 is made up of the solar insulation coating of the present invention.

In the solar insulation film 20 being made up of above-mentioned solar insulation coating, nano inorganic infrared ray absorbing barrier, Nano inorganic ultraviolet radiation absorption barrier and organic uv absorbers are engaged, and can absorb the major part in barrier sunshine Black light carry energy, for example visible light transmissivity (VLT) be 70% in the case of, at sunshine spectrum 950nm Ultrared absorptivity is more than 90%, and total solar energy rejection rate is more than 45%, and sheltering coefficient (Sc) is small, it is seen that light transmission rate It is more than 1.1 with the ratio of the total transmitance of solar energy；Meanwhile, nano zine oxide and/or nano-cerium oxide, infrared ray absorbing resistance The solar insulation film being made every agent and adhesive has the advantages that highly transparent, it is seen that light transmission rate can reach 65% with On, basic areflexia.

In a preferred embodiment, it is the energy of effective infrared light carrying absorbed in barrier sunshine, above-mentioned compound work( In ergosphere 22, the nano inorganic infrared ray absorbing barrier in nano inorganic infrared ray absorbing barrier agent dispersion is tungstenic metal Oxide nano particles, the content of the tungstenic metal oxide nanoparticles is 1~5g/m², in this application, it is seen that light is saturating The rate of mistake can reach more than 50%, meanwhile, more than 90% is reached to ultrared barrier, total solar energy rejection rate reach 35% with On, reach as high as 55%.

In a preferred embodiment, it is the energy of effective ultraviolet light carrying absorbed in barrier sunshine, above-mentioned compound work( In ergosphere 22, the content of the nano inorganic ultraviolet radiation absorption barrier in nano inorganic ultraviolet radiation absorption barrier agent dispersion is 1 ~5g/m².Further, in complex functional layer 22, the content of the organic uv absorbers is 0~5g/m², preferred content is 0.1~2g/m², the barrier to ultraviolet is reached more than 99%.

Alternatively, the thickness of the complex functional layer 22 of formation is 2~50 μm, and preferred thickness is 2~20 μm, using the thickness The one side of complex functional layer 22 can play effective iris action, on the other hand do not influence the transmission of light.

Fig. 3 is refer to, further, complex functional layer 22 has upper and lower surface, above-mentioned solar insulation film 20 Also include the mould release membrance 21 and the first of the upper surface for being sequentially located at complex functional layer 22 of the lower surface positioned at complex functional layer 22 Organic polymer basement membrane 23 and hardened wear-resistant layer 24.The solar insulation film 20 significantly simplify general solar insulation film knot Structure, with easy to operate, manufacturing procedure is few, a variety of advantages such as high yield rate, Quality Control be simple.

Wherein, the first organic polymer basement membrane 23 is used as base material film, it is desirable to high transmission rate, low haze and high intensity, The the first organic polymer basement membrane 23 for meeting above-mentioned requirements includes but is not limited to be PET basement membranes, and PET basement membrane visible light transmissivities are big In 88%, mist degree is less than 1%, and intensity is high, is preferable first organic polymer basement membrane 23.First organic polymer basement membrane 23 Thickness can be in the range of 1~5mil, and typical thickness is 1mil, or 1.5mil, or 2mil, or 2.5mil.It is used as preferred side Case, before attaching complex functional layer 22 and hardened wear-resistant layer 24 on the first organic polymer basement membrane 23, to the first organic polymer Two surfaces of thing basement membrane 23 carry out sided corona treatment or chemical treatment, to increase the surface on the surface of the first organic polymer basement membrane 23 Roughness and surface area, when attaching complex functional layer 22 and hardened wear-resistant layer 24, improve its adhesive force.

Hardened wear-resistant layer 24 as solar insulation film 20 outermost film, in solar insulation film 20 by outer masterpiece Used time, prevent solar insulation film 20 to be scratched or scratch, play stronger protective effect.Hardened wear-resistant layer 24 can be by known Material is made, and is preferably made up of organic siliconresin, and the organic siliconresin includes but is not limited to UV photo-curables organic siliconresin, heat Solidity organic siliconresin.Preparation method can use coating method, and organic siliconresin is spread evenly across into the first organic polymer The surface of basement membrane 23, after heated UV illumination, hardened wear-resistant layer 24 is formed on the surface of the first organic polymer basement membrane 23.Formed The thickness of hardened wear-resistant layer 24 be preferably 1~10 μm, more preferably 2~5 μm.It is higher resistance to have hardened wear-resistant layer 24 Intensity is ground, the Mohs' hardness of hardened wear-resistant layer 24 is preferably greater than 2H.

Mould release membrance 21 is layer protecting film, and its surface is by the processing such as silicone oil, and surface adhesion is smaller, and its role is to protect Protect complex functional layer 22 contaminated or destroyed, need to remove the mould release membrance 21 when using solar insulation film 20, expose Solar insulation film 20, is attached on glass baseplate 10, such as by complex functional layer 22 by means of the adhesion of complex functional layer 22 Shown in Fig. 5.The present invention does not limit the material of mould release membrance 21, as an example, mould release membrance 21 can using PET film, PC films, The transparent polymeric films such as PVC film.

Further, Fig. 4 is refer to, solar insulation film also includes being located between complex functional layer 22 and mould release membrance 21 Second organic polymer basement membrane 25 and adhesion layer 26, the second organic polymer basement membrane 25 and adhesion layer 26 are stacked gradually in compound work( The lower surface of ergosphere 22, so as to form the solar insulation film of another structure.Second organic polymer basement membrane 25 can be used With the identical material of the first organic polymer basement membrane 23, it is preferred that the first organic polymer basement membrane 23 and the second organic polymer Basement membrane 25 is simultaneously PET basement membranes.

Adhesion layer 26 is removing mould release membrance 21 and solar insulation film is being attached on glass baseplate 10 as glue is installed When, adhesion layer 26 is used to strengthen the second organic polymer basement membrane 25 and the adhesion of glass baseplate 10, prevents solar insulation film Come off from glass baseplate 10.It is preferred that the material of adhesion layer 26 is acrylate pressure sensitive adhesive.

In one embodiment, in the solar insulation coating for preparing complex functional layer 22, resin is selected from polyurethane Resin adhesive or polyacrylic resin adhesive, this material can not only as solar insulation coating carrier, and Certain adhesive attraction can be made it have, the organic polymer basement membrane 23, second of enhancing complex functional layer 22 and first is organic poly- Adhesion between compound basement membrane 25.

Further aspect of the present invention provides a kind of preparation method of solar insulation film 20, including accurate coating, dry and conjunction Three steps of film.

Wherein, (1) precision coating：The each component of the solar insulation coating of the present invention is carried out to be mixed to get with flowing Property solar insulation coating, by solar insulation coating and prepare the slurry of hardened wear-resistant layer 24 to be respectively coated on first organic On two surfaces of polymer-based film 23.

Specifically, nano inorganic infrared ray absorbing is obstructed into agent dispersion, nano inorganic ultraviolet radiation absorption barrier point Granular media, organic uv absorbers, resin, solvent diluent be mixed and stirred for uniformly, obtaining the sun with mobility Light insulating moulding coating, the slurry for preparing hardened wear-resistant layer 24 can be the organic siliconresin with mobility.By above-mentioned sunshine every Hot coating and organic siliconresin are equably coated on two surfaces of the first organic polymer basement membrane 23 (such as PET basement membranes) respectively On, in one embodiment, above-mentioned solar insulation coatings are in the wet film behind the surface of the first organic polymer basement membrane 23 Thickness is 5~100 μm, and typical thickness is 20~60 μm, prepares the slurry coats of hardened wear-resistant layer 24 in the first organic polymer Wet-film thickness behind the surface of thing basement membrane 23 is 1~50 μm, and typical thickness is 5~20 μm.

In a preferred embodiment, accurate coating can be using dip coated, scraper for coating, lip type coating, slit extruding The coating methods such as coating, slope streaming extrusion coated or dropping curtain formula extrusion coated.

For another thermal isolation film 20 with multiple layer polymer based film structure as shown in Figure 4, walked more than completing After rapid, the second organic polymer basement membrane 25 is fitted in into the surface of complex functional layer 22, complex functional layer 22 is sandwiched in two layers of polymer In the middle of thing basement membrane.Then it is coated with another layer polypropylene on the surface of the second organic polymer basement membrane 25 away from complex functional layer 22 Acid resin pressure sensitive adhesive formation adhesion layer 26.

(2) dry：To being coated respectively with solar insulation coating on two surfaces and preparing the slurry of hardened wear-resistant layer 24 The first organic polymer basement membrane 23 be dried, solar insulation coating obtains complex functional layer 22 after drying, and prepares hardening The slurry of wearing layer 24 obtains hardened wear-resistant layer 24 after drying.

Specifically, can be by the way that two sides to be coated respectively with to the first organic polymer of solar insulation coating and slurry Basement membrane 23 is at the uniform velocity by a baking oven, and the baking oven can be blowing-type, infrared type, microwave type baking oven, when the first organic polymer When basement membrane 23 is by baking oven, the solvent in solar insulation coating and the slurry for preparing hardened wear-resistant layer 24 is evaporated, and is formed Complex functional layer 22 and hardened wear-resistant layer 24.It should be noted that when solar insulation coating or preparing hardened wear-resistant layer 24 When slurry needs to use UV photocurings, in baking oven or at its opening a ultraviolet illumination device can be set to enter above-mentioned material Row solidification.

It is after complex functional layer 22 and hardened wear-resistant layer 24 are dried, then by second for thermal isolation film 20 as shown in Figure 4 Organic polymer basement membrane 25 fits in the surface away from the first organic polymer basement membrane 23 of complex functional layer 22, then again the The surface painting polypropylene resin pressure-sensitive glue formation adhesion layer 26 of two organic polymer basement membranes 25, then under the same conditions, enters Row drying.

It is appreciated that the complex functional layer 22 and hardened wear-resistant layer 24 of the present invention can use two coating heads, it is organic first Two surfaces of polymer-based film 23 are coated with simultaneously, then dry to form solar insulation film 20 as described in Figure 3.Then, Second organic polymer basement membrane 25 is fitted in the surface away from the first organic polymer basement membrane 23 of complex functional layer 22, then Again in the surface painting polypropylene resin pressure-sensitive glue formation adhesion layer 26 of the second organic polymer basement membrane 25, to be formed such as Fig. 4 institutes The solar insulation film 20 shown.

(3) film is closed：Mould release membrance 21 is attached on the side away from the first organic polymer basement membrane 23 of complex functional layer 22, Obtain solar insulation film 20.

Or on the side away from the first organic polymer basement membrane 23 of complex functional layer 22, compound another layer organic poly- Compound basement membrane 25, attaches mould release membrance 21, obtains solar insulation film 20.

By exposed in the exposed side of complex functional layer 22, or in adhesion layer 26 (such as acrylic resin pressure-sensitive adhesive layer) Side capping mould release membrance 21, the surface of the side can be protected not to be contaminated and destroy.

It is wound on core, is formed into by coiling machine it is possible to further which the solar insulation film 20 obtained after film will be closed The finished product of volume.

Compared with existing widely used magnetron sputtering embrane method, because magnetron sputtering embrane method needs to use two Layer PET basement membranes, magnetron sputtering technique working condition requires higher, along with the complicated membrane structure and system corresponding with this technology Standby technology, causes such product cost height, low production efficiency, product qualified rate low, so that such product price of in the market It is high, it is difficult to be widely applied on building glass.In the above-mentioned preparation method of the present invention, with the technique of precision coating, replace For observing and controlling sputtering technology, preparation process condition requires relatively low so that preparation difficulty is relatively low, yield rate is higher, advantageously reduces life Produce cost.

Fig. 6 is refer to, further aspect of the present invention provides a kind of solar insulation glass, and the solar insulation glass includes glass Glass base material 10 and the solar insulation coating 30 on glass baseplate 10, wherein, solar insulation coating 30 is by the present invention's Solar insulation coating is made.

Alternatively, the resin of solar insulation coating is selected from organic siliconresin, and organic siliconresin includes but is not limited to be UV Solidified resin or heat reactive resin, by solar insulation coating application on glass baseplate 10 after, can by ultraviolet light or Heating means make solar insulation paint solidification formation solar insulation coating 30, the solar insulation coating 30 itself after solidification With high rigidity and abrasion resistance properties, its case hardness is up to 3H.

Alternatively, solar insulation coating 30 can be by using at least one in spraying, roller coating, brushing, dip-coating, printing The method of kind forms the surface that solar insulation coating is applied to glass baseplate 10.

The present invention does not limit the particular type of glass baseplate 10, in one embodiment, glass baseplate 10 be common white glass, One kind in safety glass, coated glass.

Further aspect of the present invention provides the solar insulation glass of a kind of pair of glass single-chamber, the solar insulation of this pair of glass single-chamber Glass includes shape between two panels glass and the ageing-resistant glue by the two panels glass-encapsulated one entirety of formation, two sheet glass Into gas blanket, at least a piece of in two sheet glass is the solar insulation glass using the present invention.

Further aspect of the present invention provides a kind of solar insulation glass of three glass two-chamber, the solar insulation of the three glass two-chamber Glass include three sheet glass and three sheet glass is encapsulated in the ageing-resistant glue to form an entirety, three sheet glass adjacent two Form gas blanket between sheet glass, formed in three glass double cavity structures, three sheet glass it is at least a piece of be using the present invention too Sunlight heat-protecting glass.

Embodiment 1：

Respectively by 200g wolframic acids, 113g cesium hydroxides, 833g citric acids, 50g winter propylhomoserins are added to 1067mL water and 267mL Reaction slurry is formed in the mixture of ethanol, this slurry is can heat up, reacted in the high-pressure reactor of temperature control, in stirring In the state of, with 3 DEG C/min speed, 300 DEG C are progressively warming up to, and 12 hours are incubated at this temperature, then force drop Temperature arrives room temperature.Slurry is then taken out, slurry is centrifuged to remove the foreign ion in slurry；Gained filter cake is disperseed In 500mL water, separation is then centrifuged for；Gained filter cake is scattered in 500mL ethanol again, separation, ethanol washing is then centrifuged for Process has progress altogether twice, and gained filter cake can directly be dried, crush, and obtain power-product.

Fig. 7 is refer to, the pattern and structure of the nano particle are observed using SEM (SEM), from its SEM figures It can be seen that the average grain diameter of the nano particle is about 20~30nm.

Fig. 8 is refer to, X-ray diffraction (XRD) figure of the nano particle and standard JCPDS cards are contrasted, gained nanometer Particle crystal formation is hexagonal phase；

Fig. 9 is refer to, from power spectrum (EDX) analysis result of the nano particle, the composition composition of the particle can be calculated, It is shown in Table 1.

Table 1

Element	O	K	Sn	Cs	W	It is total
							Wt%	16.79	0.01	0.1	19.11	63.98	100

Figure 10 is refer to, using X-ray diffraction analysis (XPS), for W 4f_7/2In 34.2eV (W⁵⁺) and 35.5eV (W⁶ ⁺) tunable band-gap, W in this particle⁵⁺/W⁶⁺=22:78.

By above analysis result, gained nano particle is the tungsten oxide crystallization containing caesium, and its molecular formula is Cs_0.3WO₃, it is brilliant Type is hexagonal phase, W⁵⁺/W⁶⁺=22:78.

Embodiment 2：

Respectively by 200g wolframic acids, 113g cesium hydroxides, 551g citric acids, 11.5g sodium borohydrides (NaBH₄), it is added to In the mixture of 1067mL water and 267mL ethanol, or in 1334mL water, reaction slurry is formed, this slurry is can heat up, temperature control High-pressure reactor in reacted, in the state of stirring, with 3 DEG C/min speed, be progressively warming up to 300 DEG C, and herein At a temperature of be incubated 12 hours, then forced cooling is to room temperature.Slurry is then taken out, slurry is centrifuged to remove material Foreign ion in slurry；Gained filter cake is scattered in 500mL water, separation is then centrifuged for；Gained filter cake is scattered in 500mL again In ethanol, separation is then centrifuged for, ethanol wash process has progress altogether twice, and gained filter cake can directly be dried, crush, and obtain Power-product.

Gained nano particle is the tungsten oxide crystallization containing caesium, and its molecular formula is Cs_0.3WO₃, crystal formation is hexagonal phase, W⁵⁺/W⁶⁺ =22:78；The pattern and structure of the nano particle, the average grain of the nano particle are observed using SEM (SEM) Footpath is about 20~30nm.

Embodiment 3：

Respectively by 200g wolframic acids, 113g cesium hydroxides, 551g citric acids, 11.5g hydrazine hydrates (N₂H₄·H₂O), it is added to In the mixture of 1067mL water and 267mL ethanol, or in 1334mL water, reaction slurry is formed, this slurry is can heat up, temperature control High-pressure reactor in reacted, in the state of stirring, with 3 DEG C/min speed, be progressively warming up to 300 DEG C, and herein At a temperature of be incubated 12 hours, then forced cooling is to room temperature.Slurry is then taken out, slurry is centrifuged to remove material Foreign ion in slurry；Gained filter cake is scattered in 500mL water, separation is then centrifuged for；Gained filter cake is scattered in 500mL again In ethanol, separation is then centrifuged for, ethanol wash process has progress altogether twice, and gained filter cake can directly be dried, crush, and obtain Power-product.

Embodiment 4：

Respectively by 200g wolframic acids, 113g cesium hydroxides, 551g citric acids, 11.5g sodium borohydrides (NaBH₄), 55g hydroxides Tin (Sn (OH)₂), in the mixture for being added to 1067mL water and 267mL ethanol, or in 1334mL water, reaction slurry is formed, this Slurry is can heat up, reacted in the high-pressure reactor of temperature control, in the state of stirring, with 3 DEG C/min speed, progressively It is warming up to 300 DEG C, and is incubated 12 hours at this temperature, then forced cooling is to room temperature.Slurry is then taken out, slurry is entered Row centrifuges to remove the foreign ion in slurry；Gained filter cake is scattered in 500mL water, separation is then centrifuged for；By gained Filter cake is scattered in 500mL ethanol again, is then centrifuged for separation, and ethanol wash process has progress altogether twice, and gained filter cake can be straight Connect and be dried, crush, obtain power-product.

Figure 11 is refer to, the pattern and structure of the nano particle, the nanometer are observed using SEM (SEM) The average grain diameter of grain is about 20~30nm.

It refer to Figure 12：From power spectrum (EDX) analysis result of the nano particle, can calculate the particle into packet Into being shown in Table 2.

Table 2

Element	O	K	Sn	Cs	W	It is total
							Wt%	16.47	0.00	11.62	17.00	54.91	100

It refer to Figure 13：Using X-ray diffraction analysis (XPS), for W 4f_7/2In 34.2eV (W⁵⁺) and 35.5eV (W⁶ ⁺) tunable band-gap, W in this particle⁵⁺/W⁶⁺=16:84.

Analyzed more than, gained nano particle is the tungsten oxide crystallization containing tin, caesium, its molecular formula is Sn_0.3Cs_0.43WO_3.3, crystal formation is hexagonal phase, W⁵⁺/W⁶⁺=20:80；The nano particle is observed using SEM (SEM) Pattern and structure, the average grain diameter of the nano particle is about 20~30nm.

Embodiment 5：

Respectively by 200g ammonium paratungstates, 125g cesium hydroxides, 528g citric acids, 85g ASPs are added to 867mL water In the mixture of 667mL alcohol, or in 1334mL water, reaction slurry is formed, this slurry is can heat up, the reaction under high pressure of temperature control Reacted in device, in the state of stirring, with 3 DEG C/min speed, be progressively warming up to 300 DEG C, and be incubated at this temperature 12 hours, then forced cooling is to room temperature.Slurry is then taken out, slurry is centrifuged to remove the impurity in slurry Ion；Gained filter cake is scattered in 500mL water, separation is then centrifuged for；Gained filter cake is scattered in 500mL ethanol again, so After centrifuge, ethanol wash process have altogether progress twice, gained filter cake can directly be dried, crush, and obtain power-product.

Gained nano particle is the tungsten oxide crystallization containing tin, caesium, and its molecular formula is Cs_0.3WO_3.0, crystal formation is hexagonal phase, W⁵⁺/W⁶⁺=22:78；The pattern and structure of the nano particle are observed using SEM (SEM), the nano particle Average grain diameter is about 20~30nm.

Embodiment 6：

By in embodiment 1-5, the filter cake of three washings of process obtained by any embodiment preparation disperses in ethanol again, Solid content is 8%, and 65 DEG C are heated in three-necked flask, is stirred, and maintain the reflux for.By 10% mass ratio of solid content, Silane coupling reagent KH-570 (3- (methacryloxypropyl) propyl trimethoxy silicane) is weighed, and 10 times are diluted with ethanol, then It is added in three-necked flask.Keep 65 DEG C, stirring, lower 15 hours of reflux state.By this slurry Rotary Evaporators, in decompression shape Under state, it is evaporated at 65 DEG C；Then this solid being evaporated is disperseed again with ethanol again, then with identical drying mode, dispersion It is evaporated.Then by dry solid, with 30% solid content, it is dispersed in butyl acetate, obtains transparent tungstenic metal oxidation The dispersion of thing nano particle.

Figure 14 is refer to, is detected using Horiba Particle Size Analyzers LB-550, the grading curve of this dispersion Such as Figure 14, average grain diameter is 65nm.

Embodiment 7：

The filter cake of three washings of process obtained by being prepared in embodiment 1-5, in any embodiment is dispersed in ethanol again In, solid content is 8%, and 65 DEG C are heated in three-necked flask, is stirred, and maintain the reflux for.By 10% mass ratio of solid content Example, weighs Silane coupling reagent KH-570 (3- (methacryloxypropyl) propyl trimethoxy silicane), and dilutes 10 times with ethanol, so After be added in three-necked flask.Keep 65 DEG C, stirring, lower 15 hours of reflux state.By this slurry Rotary Evaporators, in decompression Under state, it is evaporated at 65 DEG C；Then this solid being evaporated is disperseed again with ethanol again, then with identical drying mode, scattered Body is evaporated.Then by dry solid, with 30% solid content, it is dispersed in dipropylene glycol methyl ether (DPM), obtains The dispersion of bright tungstenic metal oxide nanoparticles.

Figure 15 is refer to, is detected using Horiba Particle Size Analyzers LB-550, the grading curve of this dispersion Such as Figure 15, average grain diameter is 75nm.

Embodiment 8：

The filter cake of three washings of process obtained by being prepared in embodiment 1-5, in any embodiment is dispersed in ethanol again In, solid content is 8%, and 65 DEG C are heated in three-necked flask, is stirred, and maintain the reflux for.By 10% mass ratio of solid content Example, weighs silane coupler 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH560), and dilutes 10 times with ethanol, so After be added in three-necked flask.Keep 65 DEG C, stirring, lower 15 hours of reflux state.By this slurry Rotary Evaporators, in decompression Under state, it is evaporated at 65 DEG C；Then this solid being evaporated is disperseed again with ethanol again, then with identical drying mode, scattered Body is evaporated.Then by dry solid, with 30% solid content, it is dispersed in isopropanol, obtains transparent tungstenic metal oxidation The dispersion of thing nano particle.

Figure 16 is refer to, is detected using Horiba Particle Size Analyzers LB-550, the grading curve of this dispersion Such as Figure 16, average grain diameter is 68nm.

Embodiment 9：

The filter cake of three washings of process obtained by being prepared in embodiment 1-5, in any embodiment is dispersed in ethanol again In, solid content is 8%, and 65 DEG C are heated in three-necked flask, is stirred, and maintain the reflux for.By 10% mass ratio of solid content Example, weighs silane coupler hexadecyl trimethoxy silane, and dilutes 10 times with ethanol, is then added in three-necked flask. Keep 65 DEG C, stirring, lower 15 hours of reflux state.By this slurry Rotary Evaporators, under a reduced pressure, it is evaporated at 65 DEG C； Then this solid being evaporated is disperseed again with ethanol again, then with identical drying mode, dispersion be evaporated.Then will be dry Solid, with 30% solid content, is dispersed in toluene or dimethylbenzene, obtains point of transparent tungstenic metal oxide nanoparticles Granular media.

Figure 17 is refer to, is detected using Horiba Particle Size Analyzers LB-550, the grading curve of this dispersion Such as Figure 17, average grain diameter is 73nm.

Embodiment 10：

The filter cake of three washings of process obtained by being prepared in embodiment 1-5, in any embodiment is dispersed in ethanol again In, solid content is 8%, and 65 DEG C are heated in three-necked flask, is stirred, and maintain the reflux for.By 10% mass ratio of solid content Example, weighs silane coupler 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH560), and dilutes 10 times with ethanol, so After be added in three-necked flask.Keep 65 DEG C, stirring, lower 3 hours of reflux state.This slurry is centrifuged, filter cake is dispersed in again In the water of 1/2 raw material slurry product, and centrifuge again.Moisture is dissipated, centrifugal separation processes are repeated twice altogether.By filter cake by containing admittedly In amount 30%, the water for being dispersed in the MEA containing 1wt%, the dispersion of transparent tungstenic metal oxide nanoparticles is obtained.

Figure 18 is refer to, is detected using Horiba Particle Size Analyzers LB-550, the grading curve of this dispersion Such as Figure 18, average grain diameter is 54nm.

Embodiment 11：

In the present embodiment, the formula of insulating glass coating is as follows：

Resin：RTU-8182 types organic siliconresin (Anqing Hao Ye resins Science and Technology Ltd.)：100 parts；

Inorganic thermal insulation nano material：The dipropyl two of obtained 30% tungstenic metal oxide nanoparticles in embodiment 7 Alcohol methyl ether (DPM) dispersion liquid, model：MTD-332DM, active ingredient (Cs_0.3WO₃)：70 parts；

Inorganic UV absorbs nano material：ZND-401PA type nano zinc oxide fluid dispersions：20 parts；

Organic uv absorbers：UV384-2(Basf)：5 parts；

Dipropylene glycol methyl ether (DPM)：30 parts.

By above component, sequentially add, stirred with homogenizer, formed with it is heat-insulated, apply every ultraviolet glass Material, this coating can be constructed in glass surface by schemes such as roller coating, brushing, showering, printings, make glass have it is heat-insulated, every purple Outer effect.

Embodiment 12：

Resin：3132 type organic siliconresins (Anqing Yue Shan resins Science and Technology Ltd.)：100 parts；

Inorganic thermal insulation nano material：The isopropanol of obtained 30% tungstenic metal oxide nanoparticles in embodiment 8 (IPA) dispersion liquid, model：MTD-335PA, active ingredient molecular formula (Sn_0.3Cs_0.43WO_3.3)：80 parts；

Inorganic UV absorbs nano material：ZND-401PA type nano zinc oxide fluid dispersions：25 parts；

Dipropylene glycol methyl ether (DPM)：30 parts.

Embodiment 13：

Thick with Lekai 2mil in the present embodiment, the PET film of two-sided sided corona treatment is basement membrane, and Surface hardened layer scuff-resistant coating is used The UV solidification glues of Ya Shilan Purerad 8264, resin adhesive is the large 3278 type acrylic acid adhesive of Shanghai letter, with embodiment 6 In 30% tungstenic metal oxide nanoparticles butyl acetate dispersion liquid be infrared ray barriers function material, model： MTD-330BA, active ingredient molecular formula (Cs_0.3WO₃)；Inorganic UV light absorber is using our companyZND- 401BA type nano zinc oxide fluid dispersions, UV absorption synergist is Basf UV384-2.Wherein, in advance by 3278/ acetic acid fourth Ester/MTD-330BA/ZND-401BA/UV384-2 is mixed to form composite function film coating material with mass ratio 100/50/70/20/5 Material, i.e. solar insulation coating, and by the filtering of 1500 mesh filter screens.

First, with 12 microns of coating device, in the basement membrane one side of A4 sizes, the UV solidification glues of Purerad 8264 are applied to Film surface, dries 2min at 50 DEG C, is then solidified with the ultraviolet lamp of 160W/cm power.After being dried after this face, with 50 microns Coating device, complex functional layer coating slurry is coated on the another side of PET basement membranes, and dry 2min at 105 DEG C.Then will 1.5mil mould release membrance invests complex function layer surface, forms complete solar insulation film finished product.This membrane structure is simple, technique It is greatly simplified, is easy to amplification, advantageously reduces cost.

Figure 19 is refer to, formula and the solar insulation film prepared by technique as more than, it is seen that light transmission rate is left 70% Ultrared absorptivity is more than 90% at the right side, sunshine spectrum 950nm, and total solar energy rejection rate is more than 45%, masking system Number (Sc) is less than 0.62.Visible light transmissivity (VLT) and the ratio of the total transmitance of solar energy are more than 1.2, meanwhile, to ultraviolet The rejection rate in linear light area is more than 99%, and case hardness is 3H.

Requirement according to GB-T 29061-2012 " building glass functional membrane " to solar insulation film burn-in test, is adopted Non- YW-XDLH8 types xenon lamp aging case is ground with Zhejiang, under conditions of national regulations, the ageing-resistant acceleration carried out 1200 hours is surveyed Examination, as a result shows, before and after aging, outward appearance, color do not change, it is seen that the total rejection rate of light transmission rate, solar energy and ultraviolet light Rejection rate change is respectively less than 2%.

Embodiment 14：

Thick with Lekai 2mil in the present embodiment, the PET film of two-sided sided corona treatment is basement membrane, and Surface hardened layer scuff-resistant coating is used The UV solidification glues of Ya Shilan Purerad 8264, resin adhesive is the large 3278 type acrylic acid adhesive of Shanghai letter, with embodiment 8 In 30% tungstenic metal oxide nanoparticles isopropanol dispersion liquid be infrared ray barriers function material, model：MTD- 331PA, active ingredient molecular formula is (Cs_0.3WO₃), inorganic UV light absorber is using our companyCED- 401PA type nano-cerium oxide dispersion liquids, UV absorption synergist is Basf UV-571.Wherein, in advance by 3278/ isopropanol/ MTD-331PA/ inorganic UV absorbentsCED-401PA/ organic uv absorbers UV-571 is with mass ratio 100/30/70/20/5 mixing complex function film coating materials, and by the filtering of 1500 mesh filter screens.

Figure 20 is refer to, formula and the solar insulation film prepared by technique as more than, it is seen that light transmission rate is left 65% Ultrared absorptivity is more than 90% at the right side, sunshine spectrum 950nm, and total solar energy rejection rate is more than 50%, masking system Number (Sc) is less than 0.57.Visible light transmissivity (VLT) and the ratio of the total transmitance of solar energy are more than 1.2, meanwhile, to ultraviolet The rejection rate in linear light area is more than 99%, and case hardness is 3H.

Embodiment 15：

Thick with Lekai 1mil in the present embodiment, the PET film of two-sided sided corona treatment is basement membrane, and Surface hardened layer scuff-resistant coating is used The UV solidification glues of Ya Shilan Purerad 8264, adhesive is the sub- assorted blue type acrylic acid adhesives of AroSET 951014, to implement The isopropanol dispersion liquid of 30% tungstenic metal oxide nanoparticles in example 8 is infrared ray barriers function material, model： MTD-335PA, active ingredient molecular formula is (Sn_0.3Cs_0.43WO_3.3), inorganic UV light absorber is using our companyCED-401PA type nano-cerium oxide dispersion liquids, UV absorption synergist is Basf UV-571.Wherein, in advance By the isopropanols of AroSET 951014/ (IPA)/MTD-331PA/ inorganic UV absorbentsCED-401PA is with quality Than 100/30/70/25 mixing complex function film coating materials, and by the filtering of 1500 mesh filter screens.

First, with 12 microns of coating device, in A4 sizes, the PET basement membranes one side that thickness is 1mil, by Purerad 8264 UV solidification glues are applied to film surface, and 2min is dried at 50 DEG C, are then solidified with the ultraviolet lamp of 160W/cm power.Treat this After face is dried, with 50 microns of coating devices, complex functional layer coating slurry is coated on to the another side of PET basement membranes, and at 105 DEG C Dry 2min.Then another thickness is fitted in into complex function layer surface for 1mil PET basement membranes；Again with 50 microns of smearing Device, on this another surface of PET basement membranes, the sub- assorted blue type acrylic acid adhesives of AroSET 951014 of even spread blank, Ran Hou 2min is dried at 105 DEG C；Then 1.5mil mould release membrance is invested into complex function layer surface, forms complete solar insulation film Finished product.

Figure 21 is refer to, formula and the solar insulation film prepared by technique as more than, it is seen that light transmission rate is left 65% Ultrared absorptivity is more than 90% at the right side, sunshine spectrum 950nm, and total solar energy rejection rate is more than 50%, masking system Number (Sc) is less than 0.56.Visible light transmissivity (VLT) and the ratio of the total transmitance of solar energy are more than 1.2, meanwhile, to ultraviolet The rejection rate in linear light area is more than 99%, and case hardness is 3H.

Embodiment 16：

Thick with Lekai 1mil in the present embodiment, the PET film of two-sided sided corona treatment is basement membrane, and Surface hardened layer scuff-resistant coating is used The LI-B330 surface hardeners of the clumsy credit Science and Technology Ltd. in Xiamen, resin adhesive is the large 3278 type acrylic acid viscose glue of Shanghai letter Agent, using the isopropanol dispersion liquid of the tungstenic metal oxide nanoparticles of 30% in embodiment 8 as infrared ray barriers function material Material, model：MTD-331PA, inorganic UV light absorber is using our companyZND-401PA type nano zine oxides Dispersion liquid.Wherein, in advance by 3278/ isopropanol/MTD-331PA/ inorganic UV absorbentsCED-401PA is with matter Amount is filtered than 100/30/85/25 mixing complex function film coating materials by 1500 mesh filter screens.

First, with 12 microns of coating device, in the basement membrane one side of A4 sizes, LI-B330 type surface hardeners are applied to film Surface, 2min is dried at 105 DEG C, and after being dried after this face, with 50 microns of coating devices, complex functional layer coating slurry is coated on The another side of PET basement membranes, and dry 2min at 105 DEG C.Then another thickness is fitted in into compound work(for 1mil PET basement membranes Can layer surface；Again with 50 microns of applicator, on this another surface of PET basement membranes, large 3278 type of Shanghai letter of even spread blank Acrylic acid adhesive, then dries 2min at 105 DEG C；Then 1.5mil mould release membrance is invested into complex function layer surface, shape Into complete solar insulation film finished product.

Figure 22 is refer to, formula and the solar insulation film prepared by technique as more than, it is seen that light transmission rate is left 60% Ultrared absorptivity is more than 95% at the right side, sunshine spectrum 950nm, and total solar energy rejection rate is more than 55%, masking system Number (Sc) is less than 0.52.Visible light transmissivity (VLT) and the ratio of the total transmitance of solar energy are 1.15, meanwhile, to ultraviolet The rejection rate in linear light area is more than 99%, and case hardness is 3H.

Embodiment 17：

In the present embodiment, by the glass coating in embodiment 11, the 6mm thickness in purified treatment is uniformly brushed with sponge brush Water white transparency safety glass surface, brushing amount per square meter is for 22g or so, surface drying time 45min.This sample is placed 7 days, After coating is fully cured, this coated glass is tested.Case hardness is 3H, refer to Figure 23, it is seen that light transmission rate exists Ultrared absorptivity is more than 90% at 70% or so, sunshine spectrum 950nm, and total solar energy rejection rate is more than 45%, Sheltering coefficient (Sc) is less than 0.60.Visible light transmissivity (VLT) and the ratio of the total transmitance of solar energy are more than 1.2, meanwhile, 99% is more than to the rejection rate in ultraviolet area.

Embodiment 18：

In the present embodiment, by the glass coating in embodiment 12, the 6mm thickness in purified treatment is uniformly brushed with sponge brush Water white transparency safety glass surface, brushing amount per square meter is for 22g or so, surface drying time 45min.This sample is placed 7 days, After coating is fully cured, this coated glass is tested.It refer to Figure 24, it is seen that light transmission rate is in 65% or so, the sun Ultrared absorptivity is more than 90% at light spectrum 950nm, and total solar energy rejection rate is more than 50%, and sheltering coefficient (Sc) is small In 0.56.Visible light transmissivity (VLT) and the ratio of the total transmitance of solar energy are more than 1.2, meanwhile, to ultraviolet area Rejection rate is more than 99%, and case hardness is 3H.

The sunshine barrier absorbent properties detection summarized results of the solar insulation film prepared in embodiment 13~18 is shown in Table 3, from table 3 it can be seen that the visible light transmissivity of solar insulation film prepared by the present invention is high, it is seen that light reflectivity is low, to purple The rejection rate in outer linear light area is more than 99%, and total solar energy rejection rate is more than 45%, and sheltering coefficient is smaller.

Table 3

Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art is not departing from the principle and objective of the present invention In the case of above-described embodiment can be changed within the scope of the invention, change, replace and modification.

Claims

1. a kind of preparation method of tungstenic metal oxide nanoparticles, it is characterised in that the preparation method includes following step Suddenly：

The predecessor of tungsten oxide and the predecessor of doping metals are provided, wherein the doping metals are selected from IA~VA races metal, mistake The one or more crossed in metal；

The predecessor of the tungsten oxide, the predecessor of doping metals and reducing agent, solvent are mixed to form reaction slurry, through reduction Tungstenic metal oxide nanoparticles are generated after reaction.

2. preparation method according to claim 1, it is characterised in that before the predecessor of the tungsten oxide, doping metals The mass ratio for driving thing and reducing agent is 10：1~10：1~50.

3. preparation method according to claim 1, it is characterised in that the temperature of the reduction reaction is 250~350 DEG C.

4. preparation method according to claim 1, it is characterised in that the predecessor of the tungsten oxide is selected from metatungstic acid Ammonium, positive ammonium tungstate, ammonium paratungstate, wolframic acid, tungsten silicide, tungsten sulfide, chlorine oxygen tungsten, tungsten hexachloride, tungsten tetrachloride, tungsten bromide, fluorination Tungsten, tungsten carbide, the combination of oxidation of coal tungsten or aforementioned substances.

5. preparation method according to claim 1, it is characterised in that the predecessor of the doping metals is selected from IA~VA races Hydroxide, halide, carbonate, sulfate, nitrate, formates, acetate, citrate and the transition metal of metal Hydroxide, halide, carbonate, sulfate, nitrate, formates, acetate, the group of citrate or aforementioned substances Close.

6. preparation method according to claim 1, it is characterised in that the reducing agent is selected from hydrazine hydrate, citric acid, winter ammonia The combination of acid, ASP or aforementioned substances.

7. preparation method according to claim 1, it is characterised in that the solvent be selected from water, methanol, ethanol, isopropanol, The combination of butanol or aforementioned substances.

8. a kind of tungstenic metal oxide nanoparticles, it is characterised in that the tungstenic metal oxide nanoparticles are by right It is required that the preparation method described in 1 to 7 any one is made.

9. tungstenic metal oxide nanoparticles according to claim 8, it is characterised in that described to contain tungsten metal oxidic Shown in nano particle such as formula (1)：

N_xM_yWO_zFormula (1),

Wherein, N, M are doping metals and the one or more in IA~VA races metal, transition metal, and W is tungsten, and O is oxygen, 0 ≤ x≤1,0<Y≤1,2<z<3.5.

10. tungstenic metal oxide nanoparticles according to claim 8, it is characterised in that the tungstenic metal oxidation The average grain diameter of thing nano particle is 10~100nm.