WO2013107080A1 - Vanadium dioxide powdery slurry and preparation process thereof - Google Patents
Vanadium dioxide powdery slurry and preparation process thereof Download PDFInfo
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Abstract
Provided are a vanadium dioxide powdery slurry and preparation process thereof. The vanadium dioxide powdery slurry comprises vanadium dioxide complex powder comprising vanadium dioxide nanopowders with a chemical composition of V1-xMxO2, and the surface of the vanadium dioxide nanopowders being attached to an organic-modified long chain molecule, wherein M is a doped element, and 0 ≤ x ≤ 0.5. Chemical stability and dispersibility of the vanadium dioxide powders and slurry thereof are greatly increased by organic-modifying the surface of the vanadium dioxide.
Description
本发明涉及一种二氧化钒粉体浆料及其制备方法，主要应用于制备智能节能涂层，也可用于玻璃以及外墙等隔热场合 。
The invention relates to a vanadium dioxide powder slurry and a preparation method thereof, which are mainly used for preparing intelligent energy-saving coatings, and can also be used for heat insulation applications such as glass and exterior walls.
我国的建筑能耗已经占到社会总能耗的 27.8% ，其中采暖和空调的能耗占建筑总能耗的 55%
。在现代建筑物中，玻璃占外墙的面积比例越来越大，据测算通过玻璃窗进行的热传递在冬夏季节分别占 48% 和 71% 。若采用空调调节室内温度，制冷温度提高 2
℃ ，制冷负荷减少约 20% ；制热温度调低 2 ℃ ，制热负荷减少约 30% ，通过在玻璃上贴上隔热膜或涂布隔热涂层可大幅减少能耗。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.
. In modern buildings, 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.
目前市面上的隔热膜或涂层主要还是以阻隔红外性能为主，不能响应环境变化，他们只有反射红外光的功能，而在低温下没有透过红外线的作用，不能起到智能调节室内外温差的作用，需要寻找一种可智能调节太阳热的材料，从而实现冬暖夏凉的作用。At present, 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.
二氧化钒材料具有一级相变特性，可感应环境温度变化，智能响应这一变化实现对太阳光的波段选择性透过或遮蔽。通常在环境温度低于相变温度时，含有二氧化钒的薄膜或涂层对太阳光中的可见光和中红外光几乎是完全通透的；当温度超过二氧化钒的半导体
- 金属相变温度时，二氧化钒发生相变转化为 R 相，此时材料可对中红外光选择性遮断，达到透明（可见光透过）阻热的目的。二氧化钒的半导体 -
金属相变是热诱导的可逆变化，其温度开关效应可用来对中红外线的通断进行智能控制。利用二氧化钒在红外光区高温下的低透过和低温下的高透过，可以制备完全智能的节能窗口系统。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. Usually, when the ambient temperature is lower than the phase transition temperature, 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
- When 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.
光学计算表明（ S.-Y. Li,a_ G. A. Niklasson, and C. G.
Granqvist Nanothermochromics: Calculations for VO2 nanoparticles in
dielectric hosts show much improved luminous transmittance and solar energy
transmittance modulation ， JOURNAL OF APPLIED PHYSICS 108, 063525 2010
）若能将二氧化钒纳米粉体分散于其他基质，如透明高分子，可在保留二氧化钒光学调控性能的基础上，提高可见光透过率至实用水平，可对服役中的玻璃、墙面、以及车船等运输工具的外表面进行节能改造。通过把二氧化钒材料做到纳米尺寸并和有机改性材料复合可以制备一种智能温控涂料，但由于纳米粒子比表面积小和表面自由能高，粒子之间很容易发生团聚，这种特性决定了直接把二氧化钒纳米粒
子加入到涂料中，很难真正发挥纳米材料的性能，而且容易发生团聚，影响涂层的光学性能和外观，从而限制了材料在玻璃贴膜以及透明玻璃上的应用。如中国专利申请号
200410051965
中提到了一种二氧化钒智能温控涂料，但其提到的二氧化钒粒子属于未改性二氧化钒粒子，并未涉及粒子的前处理，特别是本发明提到的二氧化钒粒子进行前分散
处理，特别是有机改性处理对于其分散性能和化学稳定性性能的提高。Optical calculations show that (S.-Y. Li, a_ GA Niklasson, and CG Granqvist Nanothermochromics: Calculations for VO 2 nanoparticles in dielectric hosts show much improved luminous transmittance and solar energy transmittance modulation , JOURNAL OF APPLIED PHYSICS 108 , 063525 2010 ) Dispersing vanadium dioxide nanopowders in other matrices, such as transparent polymers, can improve the visible light transmittance to a practical level on the basis of retaining the optical control properties of vanadium dioxide, and can be used for glass, wall surface, and Energy-saving renovation of the outer surface of vehicles such as vehicles and ships. An intelligent temperature-controlled coating can be prepared by making the vanadium dioxide material nano-sized and compounded with the organically modified material. However, due to the small specific surface area of the nano-particles and high surface free energy, agglomeration easily occurs between the particles. It is decided that 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. 200410051965, but the 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.
中国专利申请号： 200610117027.4
提及一种二氧化钒悬浮液的制备方法，其中涉及二氧化钒粉体的分散处理，但其采用的是无机改性的方法，与本发明采取的有机改性方案制备二氧化钒复合粒子有本质的不同，且发明中采用酸性或碱性条件，会破坏二氧化钒的结构
。Chinese Patent Application No.: 200610117027.4
The invention relates to a preparation method of a vanadium dioxide suspension, which relates to a dispersion treatment of vanadium dioxide powder, but adopts an inorganic modification method, and prepares vanadium dioxide composite particles with the organic modification scheme adopted by the invention. There are essential differences, and the use of acidic or alkaline conditions in the invention will destroy the structure of vanadium dioxide.
.
中国专利申请号： 200980123044.0
热变色微粒子及其分散液和制造方法以及调光性涂料、调光性膜、调光性油墨中提及了调光性涂料微粒的表面处理，但其并未提出具体改性方法，且该发明处理的是二氧化钛和二氧化钒复合粒子与本专利发明内容所涉及的二氧化钒复合粉体有本质的不同
。Chinese Patent Application No.: 200980123044.0
The surface treatment of the dimming coating particles is mentioned in the thermochromic microparticles, the dispersion thereof and the manufacturing method thereof, and the dimming coating, the dimming film, and the dimming ink, but the specific modification method is not proposed, and The invention treats that the titanium dioxide and vanadium dioxide composite particles are substantially different from the vanadium dioxide composite powders involved in the patent of the present invention.
.
应用二氧化钒粉体及二氧化钒粉体与其他物质复合制备薄膜，方法简单，便于大规模操作，不但可以用于原有玻璃窗的节能化改造，并且可以涂覆在不同衬底上，扩大二氧化钒的应用性。但是将二氧化钒粉体制备成二氧化钒浆液、形成薄膜及涂层时，要求二氧化钒粉体具有优异的分散性能和化学稳定性
。The use of 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. However, when 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.
.
在此，本发明提供一种二氧化钒复合粉体，包括化学组成为
V1-xMxO2 的二氧化钒纳米粉体，二氧化钒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 。Here, 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. Where M is a doping element, 0 ≤ x ≤ 0.5.
本发明的二氧化钒复合粉体，对二氧化钒及其掺杂纳米粉体的表面经过有机改性。它不同于一般未改性或者无机包裹和改性的二氧化钒粉体，通过有机改性剂的方式使二氧化钒表面接上有机改性长链分子，从而极大提高二氧化钒粉体的化学稳定性和分散性。应用本发明提供的二氧化钒复合粉体稳定性和分散性好，能够长期保存使用，可作为智能隔热粉体应用于制备智能节能涂层或涂料，也可用于玻璃以及外墙等隔热场合。它与一般的隔热材料不同，其在相变温度以上时可大幅阻隔红外光，而低于相变温度红外线可以高度透过，而且这种变化是可逆的，可以实现太阳热的智能调节。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. Chemical stability and dispersion. 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.
较佳地，本发明的二氧化钒复合粉体中，有机改性长链分子的含量在 0.1 ～ 50%
。更优选地，有机改性长链分子含量在 1 ～ 10%
。有机改性长链分子含量过小，则无法实现粉体表面的充分包裹；有机改性长链分子含量过大，会导致有机分子之间相互缠结，反而影响分散效果。Preferably, in the vanadium dioxide composite powder of the present invention, 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.
较佳地，有机改性长链分子链长度在 0.1nm ～ 100nm 。Preferably, the organically modified long chain molecular chain has a length of from 0.1 nm to 100 nm.
本发明涉及二氧化钒纳米粒子的有机表面改性，可以有效的提高二氧化钒及其掺杂纳米粉体的分散性和粉体的化学稳定性
。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.
.
有机改性长链分子为包括长链烷基、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、羧基化长链烷基等官能化有机长链
。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
.
本发明的二氧化钒复合粉体，通过有机改性改性剂在二氧化钒粉体表面的接枝，包裹在二氧化钒粉体表面，从而可以改变二氧化钒的表面特性，根据所选基团的不同，可以增加二氧化钒复合粒子在不同溶剂里的分散性能，扩展了二氧化钒粒子在智能温控涂料或涂层中的用途。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.
较佳地， 本发明的二氧化钒复合粉体中的二氧化钒纳米粉体为金红石相，相转变温度在 -20 ～ 70
℃可调。金红石相二氧化钒所占的比例可以高达 80% ，甚至可以达到 100%
。该二氧化钒纳米粉体具有一级相变特性，可感应环境温度变化，智能响应这一变化实现对太阳光的波段选择性透过或遮蔽。通常在环境温度低于相变温度时，含有二氧化钒的薄膜或涂层对太阳光中的可见光和中红外光几乎是完全通透的；当温度超过二氧化钒的半导体
- 金属相变温度时，二氧化钒发生相变转化为 R 相，此时材料可对中红外光选择性遮断，达到透明（可见光透过）阻热的目的。二氧化钒的半导体 -
金属相变是热诱导的可逆变化，其温度开关效应可用来对中红外线的通断进行智能控制。Preferably, 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. Usually, when the ambient temperature is lower than the phase transition temperature, 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
- When 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.
在本发明中规定的掺杂元素 M 可以是元素周期表中钒附近的 21 ～ 30
过渡元素、锡及其附近的元素以及钨、钼、钌、铌等元素中的一个或者任意组合。其中，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。优选的掺杂元素为钨、钼、铋、锡、铁、锌和钛。The doping element M specified in the present invention may be 21 to 30 near vanadium in the periodic table.
The transition element, tin and elements in the vicinity thereof, and one or any combination of elements such as tungsten, molybdenum, niobium, tantalum and the like. Among them, 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.
采用上述掺杂元素，可以控制掺杂二氧化钒粉体尺寸和形貌，所用的掺杂元素同样也能调控二氧化钒的相转变温度。By using the above doping elements, 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.
在本发明中，掺杂二氧化钒粉体优选为颗粒状，且颗粒的长径比为 1:1 ～ 10:1 ，优选为 1:1 ～
5:1 ，更优选为 1:1 ～ 2:1 。颗粒尺寸在至少一个维度上不大于 1um ，优选在至少一个维度上不大于 100nm ，更优选在三个维度上均不大于
100nm ，最优选在三个维度上均不大于 70nm 。所述颗粒状可以为例如近球形、椭圆形、雪花形、立方形、片形等。In the present invention, 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.
具有上述尺寸和形貌的二氧化钒粉体的分散性更好。经过改性后的复合粉体的分散性也将进一步得到提高。The vanadium dioxide powder having the above size and morphology has better dispersibility. The dispersibility of the modified composite powder will be further improved.
本申请还提供一种二氧化钒复合粉体的制备方法，包括工序（1）将二氧化钒纳米粉体分散于分散介质中，得混合物 A
；（2）在所述混合物 A 中加入分散助剂和用于形成二氧化钒粉体表面有机改性长链分子的有机改性剂，搅拌至充分混合均匀得混合物 B
；（3）将混合物B干燥制得有机改性的二氧化钒复合粉体。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) Drying the mixture B to obtain an organically modified vanadium dioxide composite powder.
二氧化钒粉体可以为金红石相二氧化钒纳米粒子或掺杂金红石相二氧化钒纳米粒子。可以是根据公开专利
2010PA011267CN 所提供的方法制备，也可以是其他已知的方法制备的金红石相二氧化钒纳米粒子或掺杂金红石相二氧化钒纳米粒子。粉体颗粒尺寸优选在
200nm
以下。粉体的形貌可以是颗粒、纳米棒及雪花状粒子。若制备掺杂金红石相二氧化钒纳米粒子，在掺杂元素前可采用碱性试剂处理前驱体（四价钒离子水溶液），可以得到尺寸和形貌可控的二氧化钒粉体尺寸（在至少一个维度上不大于
1um ）和形貌（颗粒状，长径比不大于 10:1
），制备的二氧化钒粉体晶粒尺寸小，粒径均一，且晶型稳定，其在水、分散剂（例如聚乙烯吡咯烷酮）中分散性好，易于涂覆在玻璃等基体上，适于制备二氧化钒粉体的薄膜和涂层。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. If the doped rutile phase vanadium dioxide nanoparticles are prepared, 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. For the preparation of films and coatings of vanadium dioxide powder.
本发明提供的二氧化钒复合粉体的制备方法，工序（2）中加入的分散助剂可以为聚乙烯醇，聚乙烯吡咯烷酮、有机改性聚硅氧烷二丙二 醇单甲醚溶液、
有机硅表面活性剂或含氟表面活性剂或业内共知的分散助剂中的一种或几种。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.
本发明提供的二氧化钒复合粉体的制备方法，工序（2）中加入的有机改性剂可以是硬脂酸、聚丙烯酸，硅烷偶联剂、铝酸酯偶联剂或
钛酸酯偶联剂等有机改性剂。优选为含高分子长链的硅烷偶联剂。The method for preparing the vanadium dioxide composite powder provided by the invention, the organic modifier added in the step (2) may be stearic acid, polyacrylic acid, a silane coupling agent, an aluminate coupling agent or
An organic modifier such as a titanate coupling agent. A silane coupling agent containing a long polymer chain is preferred.
通过偶联剂的方式可以使二氧化钒表面接有机长链分子，从而极大提高二氧化钒粉体的化学稳定性和分散性 。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.
本发明提供的二氧化钒复合粉体的制备方法中所用的分散介质可以是乙醇，异丙醇、氯仿、二甲基甲酰胺、二甲基亚砜二氯乙烷或丙酮等惰性溶剂中的一种或几种。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.
在惰性介质中进行有机改性，可以防止二氧化钒的变性，提高粉体的化学稳定性 。Organic modification in an inert medium prevents the vanadium dioxide from denaturation and improves the chemical stability of the powder.
本发明提供的二氧化钒复合粉体的制备方法，制备工艺创新，通过有机改性剂的有机表面改性过程，可以有效的提高二氧化钒（ 二氧化钒
）及其掺杂纳米粉体的分散性和化学稳定性。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.
此外，本发明还提供一种包括本发明的二氧化钒复合粉体的二氧化钒粉体浆料。Further, the present invention provides a vanadium dioxide powder slurry comprising the vanadium dioxide composite powder of the present invention.
其中， 本发明提供的二氧化钒粉体浆料可以具备，（1）二氧化钒复合粉体，其包括化学组成为
V1-xMxO2 的二氧化钒纳米粉体，且所述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 ；以及（2）分散介质。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.
本发明的二氧化钒粉体浆料中， 二氧化钒复合粉体和分散介质 重量比可以为 1:1~1:1000
。优选地，二氧化钒复合粉体与分散介质的重量比为 1:5~1:500 。更优选地为 1:10~1:100 。通过本发明制备的二氧化钒复合粉体在0 ~50 重量
% 范围内都可以有效分散。若从智能涂层的应用角度来看， 0.5~10 重量 % 的范围更优选。含量过高会影响涂层的透光率，过低则难以发挥涂层的智能隔热效果。
In the vanadium dioxide powder slurry of the present invention, the weight ratio of the vanadium dioxide composite powder to the dispersion medium may be 1:1~1:1000
. Preferably, the weight ratio of the vanadium dioxide composite powder to the dispersion medium is 1:5 to 1:500. More preferably, it is 1:10~1:100. The vanadium dioxide composite powder prepared by the invention has a weight of 0 to 50
It can be effectively dispersed within the % range. From the point of view of the application of the smart coating, a range of 0.5 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.
又，可以选择去离子水、乙醇、丙醇、异丙醇、乙酸乙酯、甲苯、丁酮中的一种或几种作为本发明二氧化钒粉体浆料中的分散介质 。 Further, 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.
此外，本发明的二氧化钒复合粉体浆料还可以包括分散助剂，该分散助剂可以是选自聚丙烯酸盐、聚丙烯酰胺、多聚磷酸盐、聚乙烯醇、聚乙烯吡咯烷酮、改性聚酯，改性聚氨酯和改性丙烯酸分散剂中的一种或几种
。In addition, 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
.
此外，本发明还提供用于制备本发明的二氧化钒粉体浆料的制备方法 。Further, the present invention provides a process for producing a vanadium dioxide powder slurry of the present invention.
本发明提供的二氧化钒粉体浆料的制备方法中，可以先将二氧化钒复合粉体加入分散介质中进行预分散，然后加入所述分散剂、混合均匀制得所述二氧化钒粉体浆料
。In the method for preparing a vanadium dioxide powder slurry provided by the present invention, the vanadium dioxide composite powder may be firstly added to a dispersion medium for pre-dispersion, and then the dispersant is added and uniformly mixed to obtain the vanadium dioxide powder. Body slurry
.
本发明的二氧化钒复合粉体、以及包括该粉体的二氧化钒粉体浆料，
可应用于制备智能节能涂层或涂料，制备的涂层透明度高，雾度低、耐老化能力强，主要应用于薄膜，编织物等柔性材料，也可用于玻璃以及外墙等隔热场合 。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.
图 1 为二氧化钒粉体表面未经有机改性的二氧化钒粉体的透射电镜图；Figure 1 is a transmission electron micrograph of vanadium dioxide powder with no organic modification on the surface of vanadium dioxide powder;
图 2 为二氧化钒粉体表面经有机改性的二氧化钒复合粉体的透射电镜图。Figure 2 is a transmission electron micrograph of the organically modified vanadium dioxide composite powder on the surface of vanadium dioxide powder.
以下，参照附图，并结合下属实施方式进一步说明本发明。Hereinafter, the present invention will be further described with reference to the accompanying drawings in conjunction with the embodiments.
二氧化钒材料具有一级相变特性，可感应环境温度变化，智能响应这一变化实现对太阳光的波段选择性透过或遮蔽。将二氧化钒纳米粉体分散于其他基质，如透明高分子，可在保留二氧化钒光学调控性能的基础上，提高可见光透过率至实用水平，可对服役中的玻璃、墙面、以及车船等运输工具的外表面进行节能改造。但由于纳米粒子比表面积小和表面自由能高，粒子之间很容易发生团聚，这种特性决定了直接把二氧化钒纳米粒子加入到涂料中，很难真正发挥纳米材料的性能，而且容易发生团聚，影响涂层的光学性能和外观，从而限制了材料在玻璃贴膜以及透明玻璃上的应用。本发明涉及二氧化钒纳米粒子的有机表面改性过程，可以有效的提高二氧化钒及其掺杂纳米粉体的分散性和粉体的化学稳定性。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. Dispersing vanadium dioxide nanopowders in other matrices, such as transparent polymers, can improve the visible light transmittance to a practical level on the basis of retaining the optical control properties of vanadium dioxide, and can be used for glass, wall surface, and Energy-saving renovation of the outer surface of vehicles such as vehicles and ships. However, due to the small specific surface area of the nanoparticles and the high surface free energy, agglomeration easily occurs between the particles. This property determines that the vanadium dioxide nanoparticles are directly added to the coating, and it is difficult to truly exert the performance of the nanomaterial, and it is easy to occur. Agglomeration affects the optical properties and appearance of the coating, thereby limiting the application of the material to glass films and clear glass. The invention relates to an organic surface modification process 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.
本发明的二氧化钒复合粉体的制备方法中，包括，将二氧化钒纳米粉体分散于分散介质中，得混合物 A
的工序；在所述混合物 A 中加入分散助剂和用于形成二氧化钒粉体表面有机改性长链分子的有机改性剂，搅拌至充分混合均匀得混合物 B 的工序；将混合物 B
干燥制得有机改性的二氧化钒复合粉体的工序。In the preparation method of the vanadium dioxide composite powder of the present invention, the vanadium dioxide nano powder is dispersed in a dispersion medium to obtain a mixture A.
a step of adding a dispersing aid and an organic modifier for forming an organically modified long-chain molecule on the surface of the vanadium dioxide powder to the mixture A, stirring to a step of thoroughly mixing and obtaining a mixture B;
The step of drying to obtain an organically modified vanadium dioxide composite powder.
上述二氧化钒复合粉体的制备方法，具体地，可将重量百分比含量为 1 ～ 50 % 的二氧化钒粉体和 50 ～
99% 的分散介质先高速搅拌分散混合、并超声分散得混合物，之后在混合物中再加入分散助剂和有机改性剂，恒温 0 ～ 200
℃下搅拌，通过超声、砂磨或球磨等方式分散，再离心沉淀，一定温度下真空干燥得到有机改性的二氧化钒复合粉体 。The preparation method of the above-mentioned vanadium dioxide composite powder, specifically, the vanadium dioxide powder having a weight percentage of 1 to 50% and 50 ～
99% of the dispersion medium is firstly stirred and mixed at a high speed, and ultrasonically dispersed to obtain a mixture, 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.
其中，在将二氧化钒纳米粉体与分散介质混合的工序中，二氧化钒纳米粉体与分散介质的重量比可以为 1:1 ～
1:1000 。优选地，二氧化钒纳米粉体与分散介质的重量比为 1:5 ～ 1:100
。重量比过小时，则二氧化钒粉体同有机改性剂接触概率低，需要较长的分散时间和较大的改性剂用量；重量比过大，则不利于粉体在分散介质中的充分分散和润湿，影响后期的改性效果。Wherein, in the step of mixing the vanadium dioxide nanopowder with the dispersion medium, the weight ratio of the vanadium dioxide nanopowder to the dispersion medium may be 1:1 ～
1:1000. Preferably, the weight ratio of the vanadium dioxide nano powder to the dispersion medium is 1:5 to 1:100
. When 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.
上述二氧化钒纳米粉体表面有机改性中，有机改性剂可以是硬脂酸、聚丙烯酸，硅烷偶联剂、铝酸酯偶联剂或钛酸酯偶联剂等有机改性剂，优选为含高分子长链的硅烷偶联剂。有机改性剂加入混合物中的量可以为
0.05 ～ 5 重量 % ；优选地为 0.1 ～ 2 重量 %
。有机改性长链分子含量过小，则无法实现粉体表面的充分包裹；有机改性长链分子含量过大，会导致有机分子之间相互缠结，反而影响分散效果。
通过偶联剂的方式可以使二氧化钒表面接上有机长链分子，从而极大提高二氧化钒粉体的化学稳定性和分散性。此外，
所用分散助剂可以为聚乙烯醇，聚乙烯吡咯烷酮、有机改性聚硅氧烷二丙二醇单甲醚溶液、有机硅表面活性剂或含氟表面活性剂或业内共知的分散助剂中的一种或几种。分散助剂主要用于降低溶液的表面张力，提高溶剂在粉体表面的润湿，从而提高分散效果。分散助剂加入混合物中的量可以为
0.02 ～ 2 重量 % ； 优选地为 0.05 ～ 1 重量 %
。极少的加入量即能达到所需要的分散效果。加入过多反而会影响粉体的表面有机改性过程。In the organic modification of the surface of the vanadium dioxide nano powder, 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. In addition,
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.
本发明提供的二氧化钒粉体浆料的制备方法， 具体地，可将重量百分比含量为 1 ～ 50 %
的二氧化钒粉体加入 40 ～ 99% 的分散介质中、高速搅拌进行预分散，之后在混合物中再加入分散助剂，高速搅拌得混合均匀的二氧化钒粉体浆料
。此外还可通过超声、球磨和/或砂磨等分散方法使所述浆料混合均匀 。The preparation method of the vanadium dioxide powder slurry provided by the invention, specifically, the content of the weight percentage is 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.
. Further, the slurry may be uniformly mixed by a dispersion method such as ultrasonication, ball milling, and/or sanding.
本发明中，无论是在二氧化钒复合粉体的制备过程中还是在复合粉体浆料的制备过程中， 高速搅拌的转速可以为
1000 ～ 3000rad/min 。超声的功率可以为 50 ～ 5000 W ，频率为 21KHz 。此外，球磨机转速可以选择为 10 ～ 2000
rad/min 。又，砂磨机的转速可以为 10 ～ 2000 rad/min 。研磨介质可以选择二氧化锆球，粒径在 0.02mm ～ 50mm
，优选为小粒径的研磨介质。In the present invention, whether in the preparation process of the vanadium dioxide composite powder or in the preparation process of the composite powder slurry, 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. In addition, the ball mill speed can be selected from 10 to 2000
Rad/min. Also, 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.
应理解，本发明详述的上述实施方式，及以下实施例仅用于说明本发明而不用于限制本发明的范围。采用的原料、试剂可以通过购买市售原料或传统化学转化方式合成制得。除非另有定义或说明，本文中所使用的所有专业与科学用语与本领域技术熟练人员所熟悉的意义相同。此外任何与所记载内容相似或等同的方法及材料皆可应用于本发明方法中。本发明的其他方面由于本文的公开内容，对本领域的技术人员而言是容易理解的。It is to be understood that the above-described embodiments of the present invention and the following examples are merely illustrative of the invention and are not intended to limit the scope of the invention. The raw materials and reagents used can be synthesized by purchasing commercially available raw materials or by conventional chemical conversion. All professional and scientific terms used herein have the same meaning as those skilled in the art, unless otherwise defined or indicated. Furthermore, any methods and materials similar or equivalent to those described may be employed in the methods of the invention. Other aspects of the invention will be readily apparent to those skilled in the art from this disclosure.
以下，通过实施例对本发明进行更加详细的说明。Hereinafter, the present invention will be described in more detail by way of examples.
如图1所示，未经有机改性的二氧化钒颗粒的形貌，粉体粒径10～100nm不等，呈团聚颗粒存在但颗粒之间较为疏松。As shown in Fig. 1, the morphology of the vanadium dioxide 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.
实施例 1Example 1
( 1 ) 二氧化钒纳米粉体的表面有机改性： (1) Surface organic modification of vanadium dioxide nanopowder:
取各组分质量如下：二氧化钒纳米粉体（掺杂钨，粒径 20~100 nm ）， 20g；乙醇（分散介质），
80 g；硅烷偶联剂（含聚乙烯醇基团，有机改性剂）， 1 g； 聚乙烯吡咯烷酮（分散助剂）， 0.05 g 。先将二氧化钒纳米粉体和分散介质在 1500
rad/min 下高速搅拌分散 30min ，并超声分散 30min ，再将分散助剂和硅烷偶联剂加入其中，在高速搅拌机上恒温 70 ℃下搅拌 2 h
，再离心沉淀， 60 ℃下真空干燥得到有机硅偶联剂改性的二氧化钒复合粉体；The quality of 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. First, 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. 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.
, the precipitate is centrifuged again, and vacuum dried at 60 ° C to obtain a vanadium dioxide composite powder modified by a silicone coupling agent;
（2）二氧化钒复合粉体浆料的制备：(2) Preparation of vanadium dioxide composite powder slurry:
取各组分质量如下：本实施例第（1）中制得的二氧化钒复合粉体， 3g；去离子水， 97.95
g；改性丙烯酸分散剂， 0.05 g；将有机改性纳米粉体加入去离子水高速搅拌预分散 5min ，再加入分散剂超声分散 30min ，在高速搅拌机上搅拌处理 1
h ，得到二氧化钒及其掺杂纳米粉体浆料。本实施例中所得到的二氧化钒复合粉体及其浆料的主要性能见表 1 。The quality of each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 3 g; deionized water, 97.95
g; modified acrylic dispersant, 0.05 g; the organic modified nano-powder is added to deionized water for high-speed stirring pre-dispersion for 5 min, then dispersing agent is added for ultrasonic dispersion for 30 min, and stirred on a high-speed mixer.
h, obtaining vanadium dioxide and its doped nano powder slurry. The main properties of the vanadium dioxide composite powder and its slurry obtained in this example are shown in Table 1.
如图 2 所示，经过有机表面改性的二氧化钒复合粉体的形貌，粉体粒径 10 ～ 100nm
不等，粉体因为表面包裹有机基团，粒径较未有机改性粒子略微增大，但粉体之间呈现分散状态。As shown in Fig. 2, the morphology of the organic surface-modified vanadium dioxide composite powder has a particle size of 10 to 100 nm.
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.
实施例 2Example 2
( 1 ) 二氧化钒纳米粉体的表面有机改性：(1) Surface organic modification of vanadium dioxide nanopowder:
取各组分质量如下：二氧化钒纳米粉体（不掺杂，粒径 20~60 nm ）， 10g；乙醇（分散介质）， 90
g；硬脂酸， 1 g；聚乙烯醇（分散助剂）， 0.05 g。先将二氧化钒纳米粉体和分散介质在 1500 rad/min 下高速搅拌分散 30min
，并超声分散 30min ，再将分散助剂和硬脂酸加入其中，在高速搅拌机上恒温 60 ℃下搅拌 2 h ，再离心沉淀， 60
℃下真空干燥得到有硬脂酸改性的二氧化钒纳米复合粉体；The quality of each component is as follows: vanadium dioxide nano powder (undoped, particle size 20~60 nm), 10g; ethanol (dispersion medium), 90
g; stearic acid, 1 g; polyvinyl alcohol (dispersing aid), 0.05 g. The vanadium dioxide nano powder and the dispersion medium are firstly dispersed at a high speed of 1500 rad/min for 30 minutes.
And ultrasonically dispersed for 30 min, then the dispersing aid and stearic acid were added thereto, and stirred at a constant temperature of 60 ° C for 2 h on a high-speed mixer, and then centrifuged, 60
Vacuum drying at ° C to obtain stearic acid modified vanadium dioxide nanocomposite powder;
（2）二氧化钒复合粉体浆料的制备：(2) Preparation of vanadium dioxide composite powder slurry:
取各组分质量如下： 本实施例第（1）中制得的二氧化钒复合粉体， 1g； 异丙醇， 95 g；
聚丙烯酸盐分散剂， 0.05 g。 将有机改性纳米粉体加入去离子水高速搅拌预分散 10min ，再加入分散剂超声分散 30min ，在高速搅拌机上搅拌处理 1
h ，得到二氧化钒复合粉体浆料。本实施例中所得到的二氧化钒复合粉体及其浆料的主要性能见表 1 。The quality of each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 1 g; isopropanol, 95 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.
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.
实施例 3Example 3
( 1 ) 二氧化钒纳米粉体的表面有机改性： (1) Surface organic modification of vanadium dioxide nanopowder:
取各组分质量如下： 二氧化钒纳米粉体（掺杂钨，粒径 20~100 nm ）， 15 g；
异丙醇（分散介质）， 85 g； 硅烷偶联剂（含长链烷基，有机改性剂）， 1 g；有机改性聚硅氧烷二丙二醇单甲醚溶液（分散助剂）， 0.08g。
先将二氧化钒纳米粉体和分散介质在 1000 rad/min 下高速搅拌分散 20min ，并超声分散 60min
，再将分散助剂和硅烷偶联剂加入其中，在高速搅拌机上恒温 80 ℃下搅拌 2 h ，再离心沉淀， 60
℃下真空干燥得到表面接有长链烷基的二氧化钒纳米复合粉体。Take the quality of each component as follows: vanadium dioxide nano powder (doped tungsten, particle size 20 ~ 100 nm), 15 g;
Isopropanol (dispersion medium), 85 g; silane coupling agent (containing long-chain alkyl group, organic modifier), 1 g; organically modified polysiloxane dipropylene glycol monomethyl ether solution (dispersion 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.
Then, 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 to obtain a vanadium dioxide nanocomposite powder having a long-chain alkyl group attached thereto.
（2）二氧化钒复合粉体浆料的制备：(2) Preparation of vanadium dioxide composite powder slurry:
取各组分质量如下： 本实施例第（1）中制得的二氧化钒复合粉体， 15g； 乙酸乙酯， 75 g；
改性聚酯分散剂， 2.5 g。 将有机改性纳米粉体加入去离子水高速搅拌预分散 5min ，再加入分散剂超声分散 20min ，在高速搅拌机上搅拌处理 1 h
，得到二氧化钒复合粉体浆料。本实施例中所得到的二氧化钒复合粉体及其浆料的主要性能见表 1 。 The mass of each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 15 g; ethyl acetate, 75 g;
Modified polyester dispersant, 2.5 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.
实施例 4Example 4
( 1 ) 二氧化钒纳米粉体的表面有机改性：(1) Surface organic modification of vanadium dioxide nanopowder:
取各组分质量如下： 二氧化钒纳米粉体（掺杂钼，粒径 20~100 nm ）， 25 g；
异丙醇（分散介质）， 75 g； 钛酸酯偶联剂（含环氧基团，有机改性剂）， 1 g； 聚乙烯醇（分散助剂）， 0.15g。 先将二氧化钒纳米粉体和分散介质在
1500 rad/min 下高速搅拌分散 20min ，并超声分散 60min ，再将分散助剂和钛酸酯偶联剂加入其中，在高速搅拌机上恒温 80 ℃下搅拌 2
h ，再离心沉淀， 70 ℃下真空干燥得到表面接有环氧基团的二氧化钒纳米复合粉体。Take the quality of each component as follows: 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. First, the 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.
（2）二氧化钒复合粉体浆料的制备：(2) Preparation of vanadium dioxide composite powder slurry:
取各组分质量如下： 本实施例第（1）中制得的二氧化钒复合粉体， 4g； 去离子水， 96g；
改性丙烯酸分散剂， 0.5 g。 将有机改性纳米粉体加入去离子水高速搅拌预分散 5min ，再加入分散剂超声分散 60min ，在高速搅拌机上搅拌处理 2 h
，得到二氧化钒复合粉体浆料。 本实施例中所得到的二氧化钒复合粉体及其浆料的主要性能见表 1 。The quality of each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 4 g; deionized water, 96 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.
实施例 5Example 5
( 1 ) 二氧化钒纳米粉体的表面有机改性：(1) Surface organic modification of vanadium dioxide nanopowder:
取各组分质量如下： 二氧化钒纳米粉体（掺杂钼，粒径 20~100 nm ）， 5 g；
异丙醇（分散介质）， 95 g； 铝酸酯偶联剂（含长链烷基，有机改性剂）， 0.7 g； 聚乙烯吡咯烷酮（分散助剂）， 0.04g。
先将二氧化钒纳米粉体和分散介质在 1500 rad/min 下高速搅拌分散 20min ，并超声分散 60min
，再将分散助剂和铝酸酯偶联剂加入其中，在高速搅拌机上恒温 80 ℃下搅拌 2 h ，再离心沉淀， 60 ℃下真空干燥得到表面接有长链烷基的二氧化钒纳米粉体
。Take the quality of each component as follows: vanadium dioxide nano powder (doped with molybdenum, particle size 20 ~ 100 nm), 5 g;
Isopropanol (dispersion medium), 95 g; aluminate coupling agent (containing long-chain alkyl group, organic modifier), 0.7 g; polyvinylpyrrolidone (dispersion aid), 0.04 g.
The vanadium dioxide nanopowder and the dispersion medium were stirred at a high speed of 1500 rad/min for 20 min, and ultrasonically dispersed for 60 min.
Then, the dispersing aid and the aluminate 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, and vacuum dried at 60 ° C to obtain vanadium dioxide nanometer having a long-chain alkyl group attached thereto. Powder
.
（2）二氧化钒复合粉体浆料的制备：(2) Preparation of vanadium dioxide composite powder slurry:
取各组分质量如下： 本实施例第（1）中制得的二氧化钒复合粉体， 15g； 去离子水， 75 g；
改性聚氨酯分散剂， 2.5 g。 将有机改性纳米粉体加入去离子水高速搅拌预分散 5min ，再加入分散剂超声分散 60min ，在高速搅拌机上搅拌处理 2 h
，得到二氧化钒复合粉体浆料。 本实施例中所得到的二氧化钒复合粉体及其浆料的主要性能见表 1 。The quality of each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 15 g; deionized water, 75 g;
Modified polyurethane dispersant, 2.5 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.
实施例 6Example 6
( 1 ) 二氧化钒纳米粉体的表面有机改性：(1) Surface organic modification of vanadium dioxide nanopowder:
取各组分质量如下： 二氧化钒纳米粉体（掺杂钨，粒径 20~100 nm ）， 8 g；
异丙醇（分散介质）， 92 g； 硅烷偶联剂（含卤化长链烷基，有机改性剂）， 1 g； 有机硅表面活性剂（分散助剂）， 0.06g。
先将二氧化钒纳米粉体和分散介质在 1500 rad/min 下高速搅拌分散 20min ，并超声分散 60min
，再将分散助剂和硅烷偶联剂加入其中，在高速搅拌机上恒温 80 ℃下搅拌 2 h ，再离心沉淀， 60 ℃下真空干燥得到表面接有卤化长链烷基的二氧化钒纳米粉体
。 Take the quality of each component as follows: vanadium dioxide nano powder (doped tungsten, particle size 20 ~ 100 nm), 8 g;
Isopropanol (dispersion medium), 92 g; silane coupling agent (containing halogenated long-chain alkyl group, organic modifier), 1 g; silicone surfactant (dispersing aid), 0.06 g.
The vanadium dioxide nanopowder and the dispersion medium were stirred at a high speed of 1500 rad/min for 20 min, and ultrasonically dispersed for 60 min.
Then, 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, and vacuum dried at 60 ° C to obtain a vanadium dioxide nano powder having a halogenated long-chain alkyl group attached thereto. body
.
（2）二氧化钒复合粉体浆料的制备：(2) Preparation of vanadium dioxide composite powder slurry:
取各组分质量如下： 本实施例第（1）中制得的二氧化钒复合粉体， 20g； 甲苯， 80 g；
改性聚氨酯分散剂， 3 g。 将有机改性纳米粉体加入去离子水高速搅拌预分散 5min ，再加入分散剂超声分散 60min ，在高速搅拌机上搅拌处理 2 h
，得到二氧化钒复合粉体浆料。 本实施例中所得到的二氧化钒复合粉体及其浆料的主要性能见表 1 。The quality of each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 20 g; toluene, 80 g;
Modified polyurethane dispersant, 3 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.
实施例 7Example 7
( 1 ) 二氧化钒纳米粉体的表面有机改性： (1) Surface organic modification of vanadium dioxide nanopowder:
取各组分质量如下： 二氧化钒纳米粉体（掺杂钨，粒径 20~100 nm ）， 10 g；
乙醇（分散介质）， 90 g； 硅烷偶联剂（含环氧官能团，有机改性剂）， 1 g； 含氟表面活性剂（分散助剂）， 0.06g。
先将二氧化钒纳米粉体和分散介质在 1500 rad/min 下高速搅拌分散 20min ，并超声分散 60min
，再将分散助剂和硅烷偶联剂加入其中，在高速搅拌机上恒温 80 ℃下搅拌 2 h ，再离心沉淀， 60
℃下真空干燥得到表面接有环氧官能团的二氧化钒纳米粉体。Take the quality of each component as follows: vanadium dioxide nano powder (doped tungsten, particle size 20 ~ 100 nm), 10 g;
Ethanol (dispersion medium), 90 g; silane coupling agent (containing epoxy functional group, organic modifier), 1 g; fluorosurfactant (dispersing aid), 0.06 g.
The vanadium dioxide nanopowder and the dispersion medium were stirred at a high speed of 1500 rad/min for 20 min, and ultrasonically dispersed for 60 min.
Then, 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
The vanadium dioxide nanopowder having an epoxy functional group on its surface was obtained by vacuum drying at °C.
（2）二氧化钒复合粉体浆料的制备：(2) Preparation of vanadium dioxide composite powder slurry:
取各组分质量如下： 本实施例第（1）中制得的二氧化钒复合粉体， 5g； 去离子水， 95 g；
改性丙烯酸分散剂， 1.5 g。 将有机改性纳米粉体加入去离子水高速搅拌预分散 5min ，再加入分散剂超声分散 60min ，在高速搅拌机上搅拌处理 2 h
，得到二氧化钒复合粉体浆。 本实施例中所得到的二氧化钒复合粉体及其浆料的主要性能见表 1 。The mass of each component is as follows: the vanadium dioxide composite powder prepared in the first embodiment (1), 5 g; deionized water, 95 g;
Modified acrylic dispersant, 1.5 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.
比较例 8Comparative Example 8
取上述实施例 7 第（1）中使用的未经改性的二氧化钒纳米粉体， 5 g； 去 离子， 95g；
改性丙烯酸分散剂， 1.5 g。 将有纳米粉体加入去离子水高速搅拌预分散 5min ，再加入分散剂超声分散 60min ，在高速搅拌机上搅拌处理 2 h
，得到二氧化钒纳米粉体浆料。 本比较例所制得的二氧化钒纳米粉体浆料的主要性能见表 1 。Taking the unmodified vanadium dioxide nano powder used in the above Example 7 (1), 5 g; deionized, 95 g;
Modified acrylic dispersant, 1.5 g. The 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 nano powder slurry is obtained. The main properties of the vanadium dioxide nano powder slurry prepared in this comparative example are shown in Table 1.
参看下表 1
，从该表可说明本发明提供的方法得到的有机改性二氧化钒复合粉体及其浆料，其粒径明显小于未改性的粉体， BET
比表面积要大于未改性的粉体，浆料稳定性也要明显好于未改性的粉体浆料。通过 300 ℃失重数据可以看出通过表面有机改性过程，可以在纳米粉体表面接上 5 ～
10% 的有机长链，从而极大提高二氧化钒粉体的化学稳定性和分散性。See table 1 below
From the table, the organic modified vanadium dioxide composite powder obtained by the method provided by the invention and the slurry thereof can be illustrated, and the particle size thereof is significantly smaller than that of the unmodified powder, BET
The specific surface area is larger than the unmodified powder, and the slurry stability is also significantly better than the unmodified powder slurry. Through the 300 °C weight loss data, it can be seen that the surface of the nano-powder can be connected by the surface organic modification process.
10% organic long chain, which greatly improves the chemical stability and dispersibility of vanadium dioxide powder.
表1 ：
Table 1 :
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | 比较例8 | |
| 分散介质 | 去离子水 | 异丙醇 | 乙酸乙酯 | 去离子水 | 去离子水 | 甲苯 | 去离子水 | 去离子水 |
| 改性剂 | 含水溶性长链的硅烷偶联剂 | 硬质酸 | 含油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 | 含油溶性长链的硅烷偶联剂 | 含水溶性长链的硅烷 | 未改性 |
| 动态光散射粒径（nm） | 20～100 | 50～300 | 20～150 | 50～150 | 50～200 | 50～150 | 20～150 | 20～200 |
| BET比表面积(m3/g) | 60～70 | 45～55 | 50～60 | 50～60 | 45～55 | 50～60 | 50～60 | 40～50 |
| 粉体表面特性 | 亲水 | 亲油 | 亲油 | 亲水 | 亲水 | 亲油 | 亲水 | 亲水 |
| 300℃失重 | 12% | 4% | 10% | 8% | 7% | 8% | 9% | 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 | 不沉淀 | 不沉淀 | 沉淀较为严重 |
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Comparative Example 8 | |
| Dispersing medium | Deionized water | Isopropanol | Ethyl acetate | Deionized water | Deionized water | Toluene | Deionized water | Deionized water |
| Modifier | Silane coupling agent containing water soluble long chain | Hard acid | Oil-soluble long chain silane coupling agent | Waterborne titanate coupling agent | Aqueous aluminate coupling agent | Oil-soluble long chain silane coupling agent | Water-soluble long chain silane | Unmodified |
| Dynamic light scattering particle size (nm) | 20～100 | 50~300 | 20~150 | 50~150 | 50~200 | 50~150 | 20~150 | 20～200 |
| BET specific surface area (m 3 /g) | 60～70 | 45～55 | 50~60 | 50~60 | 45～55 | 50~60 | 50~60 | 40~50 |
| Powder surface characteristics | Hydrophilic | Lipophilic | Lipophilic | Hydrophilic | Hydrophilic | Lipophilic | Hydrophilic | Hydrophilic |
| 300 ° C weight loss | 12% | 4% | 10% | 8% | 7% | 8% | 9% | 1% |
| Slurry storage for 3 months stability | No precipitation | Slight precipitation | No precipitation | No precipitation | Slight precipitation | No precipitation | No precipitation | Precipitation is more serious |
产业应用性：
本发明二氧化钒复合粉体可应用于制备智能节能涂层或涂料，制备的涂层透明度高，雾度低、耐老化能力强，主要应用于薄膜，编织物等柔性材料，也可用于玻璃以及外墙等隔热场合。
也可以广泛应用于节能减排设备，例如节能薄膜、节能涂料、太阳能温控装置；或能源信息设备，例如，微型光电开关器件、热敏电阻、电池材料和光信息存储器件。
本发明提供的二氧化钒复合粉体的制备方法，制备工艺创新，通过有机改性剂的有机表面改性过程，可以有效的提高二氧化钒（ 二氧化钒
）及其掺杂纳米粉体的分散性和化学稳定性。 Industrial applicability : 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.
Claims (17)
- 一种二氧化钒粉体浆料，其特征在于，包括，二氧化钒复合粉体，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 ；以及分散介质。A vanadium dioxide powder slurry, comprising: 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 nano powder is connected to an organically modified long-chain molecule, wherein M is a doping element, 0 ≤ x ≤ 0.5; and a dispersion medium.
- 根据权利要求 1 所述的二氧化钒粉体浆料，其特征在于，所述有机改性长链分子含量在 0.1 ～ 50% 。The vanadium dioxide powder slurry according to claim 1, wherein the organic modified long-chain molecular content is 0.1 to 50%. .
- 根据权利要求 2 所述的二氧化钒粉体浆料，其特征在于，所述有机改性长链分子含量在 1 ～ 10% 。The vanadium dioxide powder slurry according to claim 2, wherein the organic modified long chain molecular content is from 1 to 10% .
- 根据权利要求 1 所述的二氧化钒粉体浆料，其特征在于，所述有机改性长链分子链长度在 0.1nm ～ 100nm。The vanadium dioxide powder slurry according to claim 1, wherein the organic modified long-chain molecular chain has a length of 0.1 nm. 100nm.
- 根据权利要求 1 － 4 中任一项所述的二氧化钒粉体浆料，其特征在于，所述有机改性长链分子为官能化有机长链。According to claims 1 - 4 The vanadium dioxide powder slurry according to any one of the preceding claims, wherein the organically modified long-chain molecule is a functionalized organic long chain.
- 根据权利要求 1 － 4 中任一项所述的二氧化钒粉体浆料，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。According to claims 1 - 4 The vanadium dioxide powder slurry according to any one of the preceding claims, wherein the functionalized organic long chain is a long-chain alkyl group, a polyacrylic acid group, a polyvinyl alcohol group, an epoxy group, and a long chain. Alkylamine group, halogenated long chain alkyl group, and / Or carboxylated long chain alkyl groups.
- 根据权利要求 1 ～ 4 中任一项所述的二氧化钒粉体浆料，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。The vanadium dioxide powder slurry according to any one of claims 1 to 4, wherein the powder is rutile phase vanadium dioxide nano powder, and the phase transition temperature is -20 ~ 70 °C adjustable.
- 根据权利要求 7 所述的二氧化钒粉体浆料，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。The vanadium dioxide powder slurry according to claim 7, wherein the doping element M is 21 to 30 near vanadium in the periodic table. The transition element, tin and elements in the vicinity thereof and one or any combination of tungsten, molybdenum, niobium and tantalum.
- 根据权利要求 8 所述的二氧化钒粉体浆料，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。The vanadium dioxide powder slurry according to claim 8, wherein 21 to 30 of 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.
- 根据权利要求 1 ～ 4 中任一项所述的二氧化钒粉体浆料，其特征在于，所述二氧化钒纳米粉体的颗粒尺寸在 200nm 以下。The vanadium dioxide powder slurry according to any one of claims 1 to 4, wherein the vanadium dioxide nanopowder has a particle size of 200 nm. the following.
- 根据权利要求 1 ～ 4 中任一项所述的二氧化钒粉体浆料 ，其特征在于， 浆料中二氧化钒复合粉体和分散介质的 重量比为 1:1 ～ 1:1000 。The vanadium dioxide powder slurry according to any one of claims 1 to 4, wherein a weight ratio of the vanadium dioxide composite powder to the dispersion medium in the slurry is 1:1 to 1:1000.
- 根据权利要求 11 所述的二氧化钒粉体浆料，其特征在于， 浆料中二氧化钒复合粉体和分散介质的重量比为 1:10 ～ 1:100 。The vanadium dioxide powder slurry according to claim 11, wherein the weight ratio of the vanadium dioxide composite powder to the dispersion medium in the slurry is 1:10 ～ 1:100.
- 根据权利要求 1 ～ 4 中任一项所述的二氧化钒粉体浆料 ，其特征在于，还包括分散助剂，所述分散助剂为聚丙烯酸盐、聚丙烯酰胺、多聚磷酸盐、聚乙烯醇、聚乙烯吡咯烷酮、改性聚酯，改性聚氨酯和改性丙烯酸分散剂中的一种或几种。The vanadium dioxide powder slurry according to any one of claims 1 to 4 And characterized in that it further comprises a dispersing aid, which is polyacrylate, polyacrylamide, polyphosphate, polyvinyl alcohol, polyvinylpyrrolidone, modified polyester, modified polyurethane and modified acrylic acid. One or more of the dispersing agents.
- 根据权利要求 13 所述的二氧化钒粉体浆料 ，其特征在于，所述分散助剂占所述浆料总量的 0.05 ～ 5 重量 % 。The vanadium dioxide powder slurry according to claim 13, wherein the dispersing aid accounts for 0.05 to 5% by weight of the total amount of the slurry. .
- 根据权利要求 1 ～ 4 中任一项所述的二氧化钒粉体浆料 ，其特征在于，所述分散介质包括去离子水、乙醇、丙醇、异丙醇、乙酸乙酯、甲苯、丁酮在内的一个或几种的溶剂 。The vanadium dioxide powder slurry according to any one of claims 1 to 4 It is characterized in that the dispersion medium comprises one or more solvents such as deionized water, ethanol, propanol, isopropanol, ethyl acetate, toluene, and methyl ethyl ketone.
- 一种制备权利要求1 ～ 15中任一项所述的氧化钒粉体浆料的制备方法 ，其特征在于，先将所述氧化钒复合粉体加入分散介质中进行预分散，然后加入所述分散剂、混合均匀制得所述二氧化钒粉体浆料 。Preparation method for preparing vanadium oxide powder slurry according to any one of claims 1 to 15 It is characterized in that the vanadium oxide composite powder is first added to a dispersion medium for pre-dispersion, and then the dispersant is added and uniformly mixed to obtain the vanadium dioxide powder slurry.
- 根据权利要求16所述的二氧化钒粉体浆料的制备方法 ，其特征在于，通过高速搅拌、超声、球磨和/或砂磨的分散方法使所述浆料混合均匀 。Method for preparing vanadium dioxide powder slurry according to claim 16 It is characterized in that the slurry is uniformly mixed by a high-speed stirring, ultrasonic, ball milling and/or sanding dispersion method.
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| CN108751256B (en) * | 2018-05-15 | 2020-12-29 | 清华大学 | Preparation method of high-performance lithium ion battery cathode material vanadium oxide |
| CN113773707A (en) * | 2021-10-29 | 2021-12-10 | 湖北大学 | Waterproof vanadium dioxide intelligent temperature control coating and preparation method thereof |
| CN116023800A (en) * | 2022-12-01 | 2023-04-28 | 成都先进金属材料产业技术研究院股份有限公司 | Modified vanadium dioxide nano powder and preparation method thereof |
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