阅读说明：本技术 一种钨青铜纳米复合填料及其应用 (Tungsten bronze nano composite filler and application thereof ) 是由 姚伯龙 温焱焱 范世龙 王露 曾婷 王利魁 李承东 于 2019-12-02 设计创作，主要内容包括：一种钨青铜纳米复合填料及其应用,属于汽车玻璃及建筑玻璃的制备领域。本发明利用六方钨青铜较大的隧道结构尺寸,掺杂半径较大的碱金属离子,得到结构内存在载流子,具有良好的紫外光屏蔽性能的钨青铜纳米复合填料。本发明的钨青铜纳米复合填料一方面由于具有合适的载流子浓度和局部表面等离子效应,可选择性吸收光谱；另一方面本发明的操作简单,反应温度低能耗少,反应周期短,产物分散性比较好。这样既保证了粉体具有良好的分散性,便于后续处理同时又赋予改性钨青铜粉体优良的透明隔热性。(A tungsten bronze nano composite filler and application thereof belong to the field of preparation of automobile glass and building glass. According to the invention, the tungsten bronze nano composite filler with a current carrier in the structure and good ultraviolet shielding performance is obtained by utilizing the larger tunnel structure size of the hexagonal tungsten bronze and doping the alkali metal ions with larger radius. On one hand, the tungsten bronze nano composite filler has proper carrier concentration and local surface plasma effect, and can selectively absorb spectrum; on the other hand, the method has the advantages of simple operation, low reaction temperature, less energy consumption, short reaction period and better product dispersibility. Thus, the powder has good dispersibility, is convenient for subsequent treatment and endows the modified tungsten bronze powder with excellent transparent heat insulation property.)

1. A tungsten bronze nanometer composite filler is characterized in that: the tungsten bronze nano composite filler with free carriers and good ultraviolet shielding performance in the structure is obtained by utilizing the larger tunnel structure size of the hexagonal tungsten bronze and doping alkali metal ions with larger radius.

2. The method for preparing a tungsten bronze nanocomposite filler according to claim 1, wherein: dissolving sodium tungstate dihydrate in deionized water under stirring to obtain sodium tungstate aqueous solution; rapidly adding hydrochloric acid into the sodium tungstate aqueous solution under stirring, and stirring to react to obtain yellow suspension; filtering the suspension, washing with absolute ethyl alcohol, and stirring to obtain a gelled tungstic acid/ethyl alcohol dispersion liquid; adding citric acid, barium sulfate and sodium carbonate, and carrying out solvothermal reaction; naturally cooling, centrifuging, washing with anhydrous ethanol and deionized water, removing by-products, and collecting solid precipitate; and finally, putting the solid precipitate into a vacuum drying oven for drying to obtain the tungsten bronze nano composite filler.

3. The preparation method of the tungsten bronze nano-composite filler according to claim 2, which is characterized by comprising the following specific steps: 3-4g of sodium tungstate dihydrate is dissolved in 50-60mL of deionized water under stirring to prepare 0.20-0.40mol/L sodium tungstate aqueous solution; then rapidly adding 1-2mol/L hydrochloric acid into the sodium tungstate aqueous solution under stirring, and stirring for 2-4h to obtain yellow suspension; filtering the suspension, washing with anhydrous ethanol for 3-6 times, and stirring to obtain a gelled tungstic acid/ethanol dispersion; adding 1-1.5mol/L citric acid, 1-1.5g barium sulfate and 0.10-0.30g sodium carbonate, transferring the mixed solution into a 100mL polytetrafluoroethylene high-pressure reaction kettle, and carrying out solvothermal reaction at 200 ℃ for 24-48 h; after natural cooling, centrifuging at 1000-5000rmp, washing for 3-6 times by using absolute ethyl alcohol and deionized water, removing by-products, and collecting solid precipitates; and (3) putting the solid precipitate into a vacuum drying oven, and drying for 12-24h at 50-70 ℃ and 0.08-0.10MPa to obtain solid powder, namely the tungsten bronze nano composite filler.

4. The application of the tungsten bronze nano composite filler is characterized in that: and (3) crushing the tungsten bronze nano composite filler, dispersing the crushed tungsten bronze nano composite filler in a resin solution, and curing to obtain the heat insulation coating.

5. Use of the tungsten bronze nanocomposite filler according to claim 4, wherein: carrying out ultrafine grinding on the tungsten bronze nano composite filler by using a planetary ball mill to obtain ultrafine powder with uniform particle size; weighing the superfine powder, dispersing in deionized water, and performing ultrasonic dispersion to obtain a uniform and stable dispersion; adding waterborne polyurethane and a dispersant, magnetically stirring and dissolving at room temperature, adding a photoinitiator and a functional auxiliary agent, and uniformly stirring; after UV curing, a transparent thermal barrier coating was obtained.

6. Use of the tungsten bronze nanocomposite filler according to claim 5, wherein: after the ultrafine grinding, the particle size of the obtained tungsten bronze nano composite filler powder is 10-100 nm.

7. Use of the tungsten bronze nanocomposite filler according to claim 5, wherein: the tungsten bronze nano composite filler: deionized water: dispersing agent: aqueous polyurethane: functional auxiliary agents: the mass ratio of the photoinitiator is 0.01-0.03: 10-20: 0.01-0.03: 5-10: 0.001-0.005: 0.001-0.003.

8. Use of the tungsten bronze nanocomposite filler according to claim 5, wherein: the curing is UV curing, and the curing time is 30-60 s; the drying temperature is 20-40 deg.C, and the drying time is 30-60 min.

9. Use of the tungsten bronze nanocomposite filler according to claim 5, wherein: the dispersant is PVA-2699 type dispersant; the functional auxiliary agent is one or more of a defoaming agent, a flatting agent and a wetting agent.

Technical Field

The invention relates to a tungsten bronze nano composite filler and application thereof, belonging to the field of preparation of automobile glass and building glass.

Background

With the rapid development of economy in China, the requirements of people on life quality and environmental protection are gradually improved, so that higher requirements are put forward on various properties of the transparent heat-insulating coating, and attention and wide attention of people are also attracted. At present, ATO (nano antimony tin oxide), ITO (nano indium tin oxide), AZO (nano zinc aluminum oxide) and the like are researched more, and the nano particles have better light transmittance to visible light and have a certain shielding effect to infrared rays, but the nano particles are expensive and toxic, and have poor shielding effect to near infrared rays.

For this reason, tungsten bronze, which is an inorganic infrared absorber, has been found to be of interest because of its excellent heat insulating effect. The tungsten bronze has a strong barrier rate to near infrared light, can realize high visible light transmittance, and has excellent optical performance. The nano tungsten bronze is expected to be used as a substitute material for ITO, ATO and AZO due to low price and no toxicity.

Disclosure of Invention

The invention aims to overcome the defects and provide the tungsten bronze nano composite filler and the application thereof, and the tungsten bronze nano composite filler has the characteristics of good ultraviolet shielding, visible light transmission and near infrared shielding, and is green and environment-friendly.

According to the technical scheme, the tungsten bronze nano composite filler is prepared by doping alkali metal ions with large radius by utilizing the large tunnel structure size of hexagonal tungsten bronze to obtain the tungsten bronze nano composite filler with free carriers in the structure and good ultraviolet shielding performance.

Further, sodium tungstate dihydrate is dissolved in deionized water under stirring to prepare sodium tungstate aqueous solution; rapidly adding hydrochloric acid into the sodium tungstate aqueous solution under stirring, and stirring to react to obtain yellow suspension; filtering the suspension, washing with absolute ethyl alcohol, and stirring to obtain a gelled tungstic acid/ethyl alcohol dispersion liquid; adding citric acid, barium sulfate and sodium carbonate, carrying out solvent thermal reaction, naturally cooling, centrifuging, washing with absolute ethyl alcohol and deionized water, removing by-products, and collecting solid precipitate; and finally, putting the solid precipitate into a vacuum drying oven for drying to obtain the tungsten bronze nano composite filler.

The method comprises the following specific steps: 3-4g of sodium tungstate dihydrate is dissolved in 50-60mL of deionized water under stirring to prepare 0.20-0.40mol/L sodium tungstate aqueous solution; then rapidly adding 1-2mol/L hydrochloric acid into the sodium tungstate aqueous solution under stirring, and stirring for 2-4h to obtain yellow suspension; filtering the suspension, washing with anhydrous ethanol for 3-6 times, and stirring to obtain a gelled tungstic acid/ethanol dispersion; adding 1-1.5mol/L citric acid, 1-1.5g barium sulfate and 0.10-0.30g sodium carbonate, transferring the mixed solution into a 100mL polytetrafluoroethylene high-pressure reaction kettle, and carrying out solvothermal reaction at about 200 ℃ for 24-48 h; after natural cooling, centrifuging at 1000-5000rmp, washing for 3-6 times by using absolute ethyl alcohol and deionized water, removing by-products, and collecting solid precipitates; and (3) putting the solid precipitate into a vacuum drying oven, and drying for 12-24h at 50-70 ℃ and 0.08-0.10MPa to obtain solid powder, namely the tungsten bronze nano composite filler.

The application of the tungsten bronze nano composite filler comprises the steps of crushing the tungsten bronze nano composite filler, dispersing the crushed tungsten bronze nano composite filler in a resin solution, and curing to obtain the heat-insulating coating.

Further, carrying out ultrafine grinding on the tungsten bronze nano composite filler by using a planetary ball mill to obtain ultrafine powder with uniform particle size; weighing the superfine powder, dispersing in deionized water, and performing ultrasonic dispersion to obtain a uniform and stable dispersion; adding waterborne polyurethane and a dispersant, magnetically stirring and dissolving at room temperature, adding a photoinitiator and a functional auxiliary agent, and uniformly stirring; and (5) obtaining the transparent heat insulation coating after UV curing.

Further, after the ultrafine grinding, the particle size of the obtained tungsten bronze nano composite filler powder is 10-100 nm.

Further, the tungsten bronze nanocomposite filler: deionized water: dispersing agent: aqueous polyurethane: functional auxiliary agents: the mass ratio of the photoinitiator is 0.01-0.03: 10-20: 0.01-0.03: 5-10: 0.001-0.005: 0.001-0.003.

Further, the curing is UV curing, and the curing time is 30-60 s; the drying temperature is 20-40 deg.C, and the drying time is 30-60 min.

Further, the dispersant is specifically a PVA-2699 type dispersant; the functional auxiliary agent is one or more of a defoaming agent, a flatting agent and a wetting agent.

The invention has the beneficial effects that: the tungsten bronze nano composite filler doped with metal ions prepared by the invention has good characteristics of ultraviolet light shielding, visible light transmission and near infrared shielding due to the existence of current carriers in the filler. On one hand, the tungsten bronze nano composite filler has proper carrier concentration and local surface plasma effect, and can selectively absorb spectrum; on the other hand, the method has the advantages of simple operation, low reaction temperature, less energy consumption, short reaction period and better product dispersibility. Thus, the powder has good dispersibility, is convenient for subsequent treatment and endows the modified tungsten bronze powder with excellent transparent heat insulation property.

Drawings

FIG. 1 is a graph showing the transmittance of the material prepared in example 2.

Detailed Description