CN115873437A - Heat-insulating ultraviolet-shielding phase-change material and preparation method and application thereof - Google Patents
Heat-insulating ultraviolet-shielding phase-change material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heat-insulating ultraviolet shielding phase-change material which comprises the following components in percentage by weight: 2-10% of heat-insulating ultraviolet shielding nano particle slurry and 90-96% of acrylate; 1-3% of cross-linking agent and 1-2% of photoinitiator; the heat-insulating ultraviolet-shielding nano particles are Poly Dopamine (PDA) coated tungsten bronze nano particles, have a core-shell structure and have a particle size of 30-200nm. According to the invention, the heat-insulating ultraviolet shielding nano particles are added into the phase-change material alkyl acrylate, the material has high-efficiency shielding performance on ultraviolet near infrared light and has a regulation and control effect on visible light, the inner core is used as a near infrared shielding phase and has strong near infrared absorption capacity, the shell layer can not only carry out ultraviolet absorption, but also can prevent oxygen and water vapor from contacting with the inner core, and the stability under a damp and hot environment is improved.
Description
Technical Field
The invention relates to the technical field of heat-insulating ultraviolet shielding materials, in particular to a heat-insulating ultraviolet shielding phase-change material and a preparation method and application thereof,
background
Sunlight reaching the earth's surface is mainly composed of infrared light, visible light, and ultraviolet light, wherein radiant heat is mainly concentrated in the visible and infrared regions. In addition, ultraviolet light has high energy, and a proper amount of ultraviolet light is beneficial to body health, but long-term ultraviolet radiation easily damages eyes and skin and induces diseases and even cancers, and meanwhile, ultraviolet radiation is the largest cause of outdoor aging of most polymer materials. Therefore, in order to reduce energy consumption and ultraviolet ray damage, a great deal of research is focused on a protective polymer material for transparent windows having multiple functions of heat insulation (near infrared shielding) and ultraviolet shielding. Temperature responsive materials, which are materials of different colors or optical transmittances caused by temperature changes, can be automatically generated by seasonal temperature changes, have made impressive progress in smart windows, sensors, and other on-demand devices.
Cesium doped tungsten bronze (Cs) x WO 3 CWO for short) has found practical application in laminated glass and solar control films for various architectural and automotive windows. Cs + Can be inserted into the lattice to form W 6+ And W 5+ The mixed valence of (2) shows strong localized surface plasmon resonance absorption in the near infrared range. The cesium tungsten bronze has excellent heat insulation performance (almost capable of shielding more than 80 percent of near infrared light), high transparency (visible light transmittance)>80%) and a relatively broad wavelength absorption range (capable of shielding infrared radiation from 780-2500 nm) have been the hot spots of current research. Wu et al by rational selection of Cs x WO 3 And embedded in the polymerThe thermal response type poly isopropyl acrylamide microgel in the acrylamide hydrogel matrix is used as a controllable optical switch material to prepare an intelligent window. For example, yu et al show a Cs x WO 3 Transparent wood, which has high light transmittance in the visible region and excellent near infrared light shielding ability, has potential energy-saving application.
Melanin is a biological macromolecule containing phenolic hydroxyl and amino in a structural unit, widely exists in animals and plants, and has Polydopamine (PDA) as a main component, can effectively absorb ultraviolet rays and has a light protection characteristic. Among the many properties of melanin, the most excellent and outstanding property is the optical property, i.e. the property of absorbing visible light and ultraviolet light in a monotonous broad band, which can intercept radiation reaching the human body, thus protecting the cells of the human body from the harm of light radiation. In materials science, the ultraviolet shielding material can be prepared by utilizing the properties of melanin, so that the aging of the material is delayed. Also, the light absorption ability of melanin increases monotonously from ultraviolet light to visible light. In addition, melanin has antioxidant and free radical quenching capabilities, and can be reversibly switched between an oxidized state and a reduced state. The polydopamine material can easily modify the surface of an inorganic material to form a polydopamine layer with good adhesion by virtue of excellent adhesion and simple self-polymerization conditions. The protective layer can not only improve the problem that the nano particles are easy to agglomerate, but also protect the wrapped material from being influenced by the outside. The polydopamine has strong adhesion capacity to most substrates, and can form a covalent bond through Schiff base reaction or Michael addition reaction under the alkaline condition so as to be adhered to the surface of a base material; melanin can also be bound to the surface of a substrate by non-covalent bonds such as hydrogen bonding, metal ion chelation, pi-pi stacking, coordination, and charge transfer.
The hydroxyethyl acrylate contains polyhydroxy, has hydrophilicity, is commonly used as a reactive diluent and a crosslinking agent in a radiation curing system, and can also be used as a resin crosslinking agent, a plastic and a rubber modifier. The poly (hexadecyl acrylate) is a long alkyl chain hydrophobic crystalline material, and is crystallized and melted at the temperature of 35-39 ℃. The double bonds in the acrylate monomer are polymerized to produce acrylate resin with carbon-carbon chain as main chain and high light, heat and chemical stability, so that the paint prepared with acrylate has high weather resistance, contamination resistance, acid resistance, alkali resistance and other performance.
However, in order to obtain a highly efficient heat-insulating uv-shielding composite material, some problems related to product reliability must be overcome, such as (1) inorganic nanoparticles always exhibit photocatalytic activity, capable of photo-degrading organic materials; (2) The nanoparticles are easy to agglomerate in the polymer matrix due to the strong interparticle interaction and weak interfacial interaction between the nanoparticles and the polymer; (3) Some traditional heat-insulating materials cannot give consideration to the performance of heat insulation, ultraviolet shielding and visible light regulation, and are not beneficial to the application of the traditional heat-insulating materials in real life.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a heat-insulating ultraviolet shielding phase-change material with good dispersibility and stability.
In order to achieve the purpose, the technical scheme of the invention is as follows: the invention relates to a heat-insulating ultraviolet shielding phase-change material, which consists of the following components in percentage by weight:
the heat-insulating ultraviolet-shielding nano particle slurry is Poly Dopamine (PDA) coated tungsten bronze nano particle slurry.
Further, the heat-insulating ultraviolet shielding nanoparticle slurry consists of the following components in percentage by weight:
the balance being water. MxWO 3 Represents a dark copper compound.
Further, the air conditioner is provided with a fan,the nano particles have a core-shell structure, and the particle size is 30-200nm; the tungsten bronze is one or a combination of more of ammonium tungsten bronze, cesium tungsten bronze or lithium tungsten bronze; the heat-insulating ultraviolet shielding nano particle is MxWO coated by PDA 3 Nanoparticles MxWO 3 @PDA，MxWO 3 The particle size of @ PDA is 30-200nm. MxWO 3 The nano particle is Cs x WO 3 @ PDA nanoparticles, (NH) 4 ) x WO 3 @PDA、K x WO 3 @ PDA nanoparticles, and the like.
Further, the acrylate is one or a combination of more of hydroxyethyl acrylate, cetyl acrylate or stearyl methacrylate.
The preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps: the preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps of preparing slurry of heat-insulating ultraviolet shielding nano particles and the interaction of the slurry and acrylic ester:
(1) Preparing heat-insulating ultraviolet shielding nano particle slurry: based on 100 percent of the total amount, 2 to 10 percent of MxWO is added 3 Adding the @ PDA nano particles into deionized water (the balance), sequentially adding 1-3% of KH-570 silane coupling agent, 2-5% of thickening agent and 1-2% of dispersing agent, oscillating and ultrasonically stirring until the dispersion is uniform, and magnetically stirring for 3 hours;
(2) Preparing a heat-insulating ultraviolet shielding phase-change material: adding 90-96% of acrylate into 2-10% of heat-insulating ultraviolet-shielding nano particle slurry, then adding 1-3% of cross-linking agent and 1-2% of photoinitiator, performing ultrasonic dispersion for 30 minutes, and stirring at a high speed of 1000r/min at 70 ℃ for 2 hours until the mixture is uniformly dispersed to obtain the heat-insulating ultraviolet-shielding phase-change material.
Further, M x WO 3 The preparation method of the @ PDA nano particle slurry comprises the following steps:
mixing dopamine hydrochloride and tungsten bronze according to a mass ratio of 2:1-3:2 to 100mL deionized water to form a uniform dispersion; adjusting the pH value to 8.5 by adding tris buffer solution, and reacting at 60 ℃ for 5-7 hours under the mechanical stirring of 500-1000 r/min; washing and centrifuging the product obtained in the step for many times, and drying the product in an oven at 80 ℃.
Further, in the step (1), the silane coupling agent is KH-570 silane coupling agent, and the component of the silane coupling agent is gamma- (methacryloyloxy) propyl trimethoxy silane; the thickening agent is one or a combination of more of N, N-methylene bisacrylamide, butylene diacrylate or diallyl phthalate; the dispersant is one or a combination of several of BYK-168 or polyethylene glycol.
Further, in the step (2), the cross-linking agent is one or a combination of more of trimethylolpropane triacrylate or UN-178; the photoinitiator is one or a combination of more of 2, 2-dimethyl acetophenone or diphenylethyl ketone.
The heat-insulating ultraviolet shielding phase-change material is applied to the manufacture of heat-insulating ultraviolet shielding intelligent materials.
Further, the heat-insulating ultraviolet shielding phase-change material is prepared into a coating material or a composite master batch material.
Has the advantages that: the nano-particles have good dispersibility and stability in the polymer and stronger near-infrared absorption capacity, and the shell layer can not only absorb ultraviolet, but also prevent oxygen and water vapor from contacting with the inner core, thereby improving the stability in a damp and hot environment.
Compared with the prior art, the invention has the following advantages: (1) The invention adds heat-insulating ultraviolet shielding nano particles into phase-change material alkyl acrylate, the material has high-efficiency shielding performance on ultraviolet light and near infrared light and has a regulating and controlling function on visible light, and the inner core is used as a near infrared shielding phase. Alkyl acrylate phase change materials have a large transmission modulation between room temperature and high temperatures (> 35 ℃). The alkyl acrylate phase-change material has excellent reversibility, and the performance of the phase-change material is basically unchanged and still keeps larger transmittance adjustment after multiple heating and cooling cycle tests.
(2) The heat-insulating ultraviolet shielding phase-change material is obtained by the interaction of the heat-insulating ultraviolet shielding nano particles and phase-change material acrylate. The heat-insulating ultraviolet shielding nano particles have excellent photo-thermal conversion capability, can be used as a heating source to uniformly transfer heat to the alkyl acrylate phase-change material, reduce the phase-change time and enlarge the phase-change temperature range.
(3) The phase-change material with excellent heat-insulating ultraviolet shielding performance prepared by the invention keeps higher transparency at low temperature, and the phase-change material is changed from transparent to opaque at high temperature, so that the phase-change material has great application value and prospect in the fields of intelligent windows and the like. The material can keep high visible light transmittance (more than or equal to 80 percent) at low temperature and transmit a small amount of visible light (less than or equal to 45 percent) at high temperature, and has great application potential in the field of heat-insulating ultraviolet-shielding intelligent materials.
(4) The heat-insulating ultraviolet-shielding phase change material has the advantages of smooth appearance surface, no white spots, no different spots and other defects, the transmittance to ultraviolet light is 20-46%, the transmittance to near infrared is 25-47%, the high visible light transmittance (more than or equal to 80%) is kept at room temperature, the visible light transmittance is remarkably reduced (less than or equal to 45%) when the temperature is raised to 40-50 ℃, and the phase change material is changed from transparent to opaque when the temperature is 40 ℃.
Drawings
FIG. 1 is a diagram of UV-Vis-NIR spectra of various phase change materials of the invention at different temperatures. Wherein, the curve a is a spectrogram of blank glass; curve b is the ultraviolet near infrared shielding performance graph at 25 ℃ of example 2; curve c is the UV and NIR shielding performance at 40 ℃ for example 2.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Cs of the present invention x WO 3 The preparation method of the @ PDA nano particle slurry comprises the following steps:
(1) Adding 3g of cesium tungsten bronze and 1.5g of dopamine hydrochloride into 100mL of deionized water according to the mass ratio, ultrasonically dispersing uniformly, adjusting the pH of the mixed solution to 8.5, fully stirring at room temperature for 5-7h, centrifuging, and collecting Cs x WO 3 @ PDA nanoparticle 1, washed several times with deionized water, and dried at 80 ℃.
(2) 5g of nanoparticles are added toAnd adding 1g of KH-570 silane coupling agent, 2g of N, N-methylene bisacrylamide thickening agent and 1g of BYK-168 dispersing agent into 90mL of deionized water in sequence, oscillating and ultrasonically treating for 20 minutes until the mixture is uniformly dispersed, and magnetically stirring for 3 hours. Thus obtaining Cs with the particle size of-30 nm x WO 3 @ PDA nanoparticle slurry 1.
The preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps:
preparation of 1% Cs x WO 3 @ PDA filler acrylate phase change material
80g of hydroxyethyl acrylate and 17g of hexadecyl acrylate are taken and mixed well, and then 1g of Cs prepared according to the method is added x WO 3 @ PDA slurry 1, followed by addition of 1.5g trimethylolpropane triacrylate crosslinker, 0.5g 2,2 dimethylacetophenone photoinitiator, followed by ultrasonic dispersion for 30 minutes, stirring at 1000r/min for 2-3 hours at 60 ℃ to disperse uniformly. Taking Cs x WO 3 The @ PDA acrylate slurry is uniformly sprayed on the surface of the glass, and then the glass is placed under an ultraviolet lamp to be cured for 2-3 minutes, so that the heat-insulating ultraviolet shielding phase-change material 1 is prepared.
Example 2
As shown in FIG. 1, cs of the present invention x WO 3 The preparation method of the @ PDA nano particle slurry comprises the following steps:
(1) Adding 3g of cesium tungsten bronze and 1.8g of dopamine hydrochloride into 100mL of deionized water according to the mass ratio, performing ultrasonic dispersion uniformly, adjusting the pH value of the mixed solution to 8.5, fully stirring at room temperature for 5-7h, centrifuging, and collecting Cs x WO 3 @ PDA nanoparticle 2, washed several times with deionized water and dried at 80 deg.C.
(2) Adding 7g of nanoparticles into 87mL of deionized water, sequentially adding 2g of KH-570 silane coupling agent, 3g of dipropylene butylene succinate thickener and 1g of glycol dispersant, oscillating and ultrasonically stirring for 20 minutes until the nanoparticles are uniformly dispersed, and magnetically stirring for 2 hours. Thus obtaining Cs with the particle size of-70 nm x WO 3 @ PDA nanoparticle slurry 2.
The preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps:
preparation of 5% Cs x WO 3 @ PDA filler acrylate phase change material
70g of hydroxyethyl acrylate and 22g of hexadecyl acrylate are taken and mixed thoroughly, and 5g of Cs prepared according to the method are added x WO 3 @ PDA slurry 2, followed by addition of 2g of UN-178 crosslinker, 1g of diphenylethanone photoinitiator, followed by ultrasonic dispersion for 30 minutes, and uniform dispersion at 60 ℃ with high-speed stirring at 1000r/min for 2.5 hours. Taking Cs x WO 3 The @ PDA acrylate slurry is uniformly sprayed on the surface of the glass, and then the glass is placed under an ultraviolet lamp to be cured for 2.5 minutes, so that the heat-insulating ultraviolet shielding phase-change material 2 is prepared.
FIG. 1 is a diagram of UV-Vis-NIR spectra of various phase change materials of the invention at different temperatures. The reactive phase change coating has a high transmittance in visible light and a certain shielding effect on ultraviolet near infrared light at a low temperature (curve b). After the temperature is raised, the ultraviolet visible light near infrared transmittance of the curve (c) is obviously reduced, and a good heat insulation ultraviolet shielding effect is achieved.
Example 3
Cs of the present invention x WO 3 The preparation method of the @ PDA nano particle slurry comprises the following steps:
(1) Adding 3g of cesium tungsten bronze and 2g of dopamine hydrochloride into 100mL of deionized water according to the mass ratio, ultrasonically dispersing uniformly, adjusting the pH of the mixed solution to 8.5, fully stirring at room temperature for 5-7h, centrifuging and collecting Cs x WO 3 @ PDA nanoparticle 3, washed several times with deionized water, and dried at 80 ℃.
(2) Adding 10g of nanoparticles into 81mL of deionized water, sequentially adding 3g of KH-570 silane coupling agent, 5g of phthalic acid diacrylate thickening agent and 1g of glycol dispersing agent, oscillating and ultrasonically treating for 20 minutes until the nanoparticles are uniformly dispersed, and magnetically stirring for 2-3 hours. Thus obtaining Cs with the particle size of-100 nm x WO 3 @ PDA nanoparticle slurry 3.
The preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps:
preparation of 10% Cs x WO 3 @ PDA filler acrylate phase change material
60g of hydroxyethyl acrylate, 15g of hexadecyl acrylate and 10g of stearyl methacrylate are taken and mixed thoroughly, then 10g of Cs prepared according to the method are added x WO 3 @ PDA slurry 3, followed by addition of 3g of UN-178 crosslinker, 2g of 2,2 dimethylacetophenone photoinitiator, followed by ultrasonic dispersion for 30 minutes, and uniform dispersion at 60 ℃ under high-speed stirring at 1000r/min for 2 hours. Taking Cs x WO 3 The @ PDA acrylate slurry is uniformly sprayed on the surface of the glass, and then the glass is placed under an ultraviolet lamp to be cured for 2 minutes, so that the heat-insulating ultraviolet shielding phase-change material 3 is prepared.
Example 4
Of the invention (NH) 4 ) x WO 3 The preparation method of the @ PDA nano particle slurry comprises the following steps:
(1) Adding 3g of ammonium tungsten bronze and 2.5g of dopamine hydrochloride in mass ratio into 100mL of deionized water, performing ultrasonic dispersion uniformly, adjusting the pH value of the mixed solution to 8.5, fully stirring at room temperature for 5-7h, and performing centrifugal collection (NH) 4 ) x WO 3 @ PDA nanoparticles 4, washed several times with deionized water and dried at 80 deg.C.
(2) Adding 7g of nanoparticles into 87mL of deionized water, sequentially adding 2g of KH-570 silane coupling agent, 3g of diallyl phthalate thickening agent and 1g of BYK-168 dispersing agent, oscillating and ultrasonically treating for 20 minutes until the nanoparticles are uniformly dispersed, and magnetically stirring for 2 hours. Thus obtaining Cs with the particle size of-70 nm x WO 3 @ PDA nanoparticle slurry 4.
The preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps:
preparation of 5% (NH) 4 ) x WO 3 @ PDA filler acrylate phase change material
80g of hydroxyethyl acrylate and 12g of hexadecyl acrylate are taken and mixed thoroughly, 5g of (NH) prepared according to the method are added 4 ) x WO 3 @ PDA slurry 4, then 2g of UN-178 cross-linking agent and 1g of diphenylethanone photoinitiator are added, then ultrasonic dispersion is carried out for 30 minutes, and the mixture is stirred at high speed of 1000r/min for 2-3 hours at 60 ℃ and is uniformly dispersed. To obtain (NH) 4 ) x @ PDA acrylic acidAnd (3) uniformly spraying the ester slurry on the surface of the glass, and then placing the glass under an ultraviolet lamp for curing for 2-3 minutes to prepare the heat-insulating ultraviolet shielding phase-change material 4.
Example 5
K of the invention x WO 3 The preparation method of the @ PDA nano particle slurry comprises the following steps:
(1) Adding 3g of potassium tungsten bronze and 3.5g of dopamine hydrochloride into 100mL of deionized water according to the mass ratio, ultrasonically dispersing uniformly, adjusting the pH value of the mixed solution to 8.5, fully stirring at room temperature for 5-7h, centrifuging and collecting K x WO 3 @ PDA nanoparticle 5, washed several times with deionized water, and dried at 80 ℃.
(2) Adding 7g of nanoparticles into 87mL of deionized water, sequentially adding 2g of KH-570 silane coupling agent, 3g of diallyl phthalate thickening agent and 1g of BYK-168 dispersing agent, oscillating and ultrasonically treating for 20 minutes until the nanoparticles are uniformly dispersed, and magnetically stirring for 2 hours. The obtained product has a particle size of-70 nm K x WO 3 @ PDA nano particle slurry
The preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps:
preparation of 10% K x WO 3 @ PDA filler acrylate phase change material
70g of stearyl methacrylate and 17g of cetyl acrylate are mixed thoroughly with stirring and 10g of K prepared according to the process described are subsequently added x WO 3 @ PDA slurry 5, then 2g UN-178 crosslinker, 1g diphenylethanone photoinitiator, then ultrasonic dispersion for 30 minutes, at 60 ℃ under 1000r/min high speed stirring for 3 hours to disperse evenly. Get K x WO 3 The @ PDA acrylate slurry is uniformly sprayed on the surface of the glass, and then the glass is placed under an ultraviolet lamp to be cured for 3 minutes, so that the heat-insulating ultraviolet shielding phase-change material 5 is prepared.
Comparative example 1
Lack of Cs x WO 3 Nanoparticles
Preparation of acrylate phase change material
80g of hydroxyethyl acrylate and 17g of hexadecyl acrylate are uniformly mixed, then 2g of trimethylolpropane triacrylate cross-linking agent and 1g of 2, 2-dimethyl acetophenone photoinitiator are added, ultrasonic dispersion is carried out for 30 minutes, and the mixture is uniformly dispersed by stirring at a high speed of 1000r/min for 2 to 3 hours at a temperature of 60 ℃. And (3) uniformly spraying the acrylate dispersion liquid on the surface of the glass, and then placing the glass under an ultraviolet lamp for curing for 2-3 minutes to obtain the acrylate phase-change material.
Comparative example 2
With Cs x WO 3 Nanoparticles but not phase change materials
Preparation of Cs x WO 3 Filler propylene ester material
(1) Preparation of 5% Cs x WO 3 Slurry material
5g of Cs x WO 3 Adding the nano particles into 90g of deionized water, sequentially adding 1g of KH-570 silane coupling agent, 3g of N, N-methylene bisacrylamide thickening agent and 1g of 2, 2-dimethylacetophenone photoinitiator, oscillating and ultrasonically stirring for 20 minutes until the nano particles are uniformly dispersed, and magnetically stirring for 2-3 hours.
(2) Preparation of Cs x WO 3 Acrylate material
To 93g of hydroxyethyl acrylate was added 5g of Cs x WO 3 1.5g of trimethylolpropane triacrylate cross-linking agent and 0.5g of 2, 2-dimethylacetophenone photoinitiator were added to the slurry, followed by ultrasonic dispersion for 30 minutes and uniform dispersion at 60 ℃ with high-speed stirring at 1000r/min for 2-3 hours. Taking Cs x WO 3 The @ PDA acrylate slurry is evenly sprayed on the surface of the glass and then is placed under an ultraviolet lamp to be cured for 2-3 minutes to prepare Cs x WO 3 The filler is a propylene ester material.
Comparative example 3
Is free of Cs x WO 3 The nanoparticles are also not phase change materials
Preparation of PDA filler acrylate material
(1) Preparation of 5% PDA slurry
Adding 5g of dopamine hydrochloride into 100mL of deionized water, sequentially adding 1g of KH-570 silane coupling agent, adjusting the pH to 8.5, reacting at 60 ℃ for 8h, washing and centrifuging three times, and drying in an oven at 80 ℃ for 6h to obtain PDA powder. 5g of PDA powder is added into 89mL of deionized water, ultrasonic dispersion is carried out uniformly, then 3g of N, N-methylene bisacrylamide thickener and 1g of 2, 2-dimethyl acetophenone are added, vibration and ultrasonic treatment are carried out for 20 minutes until the dispersion is uniform, and magnetic stirring is carried out for 2 hours.
(2) Preparation of PDA filler acrylate material
To 90g of hydroxyethyl acrylate was added 5g of PDA syrup, followed by addition of 1.5g of trimethylolpropane triacrylate crosslinker, 0.5g of 2, 2-dimethylacetophenone photoinitiator, followed by ultrasonic dispersion for 30 minutes, and uniform dispersion by stirring at 60 ℃ at a high speed of 1000r/min for 2 hours. And (3) uniformly spraying the PDA acrylate slurry on the surface of the glass, and then placing the glass under an ultraviolet lamp for curing for 2-3 minutes to obtain the PDA filler acrylate material.
Test examples
1. Cs obtained by comparing comparative examples and comparative examples x WO 3 The particle size of the particles in the @ PDA slurry was measured using a Malvern 2000 laser particle sizer and the results for the particle radius of the material are shown in Table 1.
TABLE 1
| Numbering | Average particle size (nm) of nanoparticles in the slurry |
| Example 1 | 41 |
| Example 2 | 78 |
| Example 3 | 93 |
| Example 4 | 87 |
| Example 5 | 126 |
| Comparative example 1 | / |
| Comparative example 2 | 37 |
| Comparative example 3 | / |
As can be seen from the results in table 1, the particle size of the prepared polydopamine-coated cesium tungsten bronze nanoparticles gradually increased with increasing dopamine content. This is because as dopamine levels increase, the level of Cs increases x WO 3 The thickness of the PDA shell layer is increased due to the self-polymerization of the particle surface, which shows that the content of dopamine can be changed to control the Cs with the core-shell structure x WO 3 The particle size of the @ PDA nano particles is convenient for being used for heat-insulating ultraviolet shielding phase change materials with different requirements. The effect of the material properties at different temperatures is shown in table 2:
TABLE 2
From the results in Table 2, it can be seen that Cs x WO 3 The @ PDA filler acrylate phase change material shows more excellent ultraviolet light and near infrared light shielding effects. The transmittance in the visible light region (400-800 nm) of the examples reached 70% or more at low temperature (-25 ℃), but when the temperature was increased to 40 ℃ or more, the visible light transmittance was significantly reducedLow (a)<45%). With respect to comparative example, with Cs x WO 3 The content of the @ PDA particles is increased, the material keeps high visible light transmittance, meanwhile, the material obviously reduces transmittance in an ultraviolet region (250-400 nm) and a near infrared region (800-2500 nm), and more excellent ultraviolet light and near infrared light shielding performance is shown.
Testing the heat insulation performance: taking 2 well-sealed white foam boxes, and placing the boxes with openings on one surface of each box in an opposite direction; a thermocouple thermometer is respectively arranged in the two boxes; the two boxes are respectively covered with blank glass and coated with the Cs cured by ultraviolet light x WO 3 The @ PDA filler acrylic ester heat-insulating ultraviolet shielding coating is placed under the irradiation of a 150W xenon lamp. And recording the temperature change in the boxes in real time, recording temperature data every 3 minutes, and comparing the temperature change in the two boxes. The insulation effectiveness test is shown in table 3:
TABLE 3
As can be seen from the data in Table 3, the temperature rising rate during the heating temperature rise process is from high to low, which is blank glass, comparative example 3, comparative example 2, comparative example 1 and example 2. It can be seen from Table 3 that only 5% of Cs was added x WO 3 The @ PDA nano particle filler acrylate phase change material is lower than blank glass in temperature by 13.6 ℃ after being heated for 21min, and shows excellent heat insulation effect which is obviously superior to that of comparative example 1, comparative example 2 and comparative example 3. The quality of the heat insulation effect is mainly influenced by two factors, firstly, whether M exists in the material or not x WO 3 The nano particles absorb near infrared light (the near infrared light accounts for 56 percent of the solar energy). Secondly, the phase-change material becomes transparent and opaque after the temperature rises, so that the transmission of visible light (the visible light accounts for 42 percent of the solar energy) is reduced, and the heat insulation effect is further achieved.
In addition, as can be seen from table 2, the phase change material maintains a high visible light transmittance at a low temperature, undergoes a phase change after temperature rise, and significantly reduces the visible light flux, thereby achieving a temperature-responsive heat insulation effect.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes and modifications made in accordance with the spirit of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (10)
1. A heat-insulating ultraviolet shielding phase-change material is characterized in that: the heat-insulating ultraviolet shielding phase-change material comprises the following components in percentage by weight:
the heat-insulating ultraviolet-shielding nano particle slurry is poly-dopamine PDA-coated tungsten bronze nano particle slurry.
2. The heat-insulating ultraviolet-shielding phase-change material as claimed in claim 1, wherein: the heat-insulating ultraviolet-shielding nanoparticle slurry consists of the following components in percentage by weight:
3. the heat-insulating ultraviolet-shielding phase-change material as claimed in claim 1, wherein: the nano particles have a core-shell structure, and the particle size is 30-200nm; the tungsten bronze is one or a combination of more of ammonium tungsten bronze, cesium tungsten bronze or lithium tungsten bronze; the heat-insulating ultraviolet shielding nano particle is MxWO coated by PDA 3 Nanoparticles MxWO 3 @PDA，MxWO 3 The particle size of @ PDA is 30-200nm.
4. The heat-insulating ultraviolet-shielding phase-change material as claimed in claim 2, wherein: the acrylate is one or a combination of more of hydroxyethyl acrylate, hexadecyl acrylate or stearyl methacrylate.
5. The method for preparing the heat-insulating ultraviolet shielding phase-change material as claimed in any one of claims 1 to 4, characterized by comprising the following steps: the preparation method of the heat-insulating ultraviolet shielding phase-change material comprises the following steps of preparing slurry of heat-insulating ultraviolet shielding nano particles and the interaction of the slurry and acrylic ester:
(1) Preparing heat-insulating ultraviolet shielding nano particle slurry: based on 100 percent of the total amount, 2 to 10 percent of MxWO 3 Adding the @ PDA nano particles into deionized water (the balance), sequentially adding 1-3% of KH-570 silane coupling agent, 2-5% of thickening agent and 1-2% of dispersing agent, oscillating and ultrasonically stirring until the dispersing is uniform, and magnetically stirring for 2-3 hours;
(2) Preparing a heat-insulating ultraviolet shielding phase-change material: adding 90-96% of acrylate into 2-10% of heat-insulating ultraviolet shielding nano particle slurry, then adding 1-3% of cross-linking agent and 1-2% of photoinitiator, performing ultrasonic dispersion for 30 minutes, and stirring at a high speed of 1000r/min at 70 ℃ for 2 hours until the mixture is uniformly dispersed to prepare the heat-insulating ultraviolet shielding phase-change material.
6. The preparation method of the heat-insulating ultraviolet shielding phase-change material as claimed in claim 5, characterized in that: m x WO 3 The preparation method of the @ PDA nano particle slurry comprises the following steps:
dopamine hydrochloride and tungsten bronze are mixed according to the mass ratio of 2:1-3:2 to 100mL of deionized water to form a homogeneous dispersion; adjusting the pH value to 8.5 by adding tris buffer solution, and reacting at 60 ℃ for 5-7 hours under the mechanical stirring of 500-1000 r/min; washing and centrifuging the product obtained in the step for many times, and drying the product in an oven at 80 ℃.
7. The preparation method of the heat-insulating ultraviolet shielding phase-change material as claimed in claim 6, wherein: in the step (1), the silane coupling agent is KH-570 silane coupling agent, and the component of the silane coupling agent is gamma- (methacryloyloxy) propyl trimethoxy silane; the thickening agent is one or a combination of more of N, N-methylene bisacrylamide, butylene diacrylate or diallyl phthalate; the dispersant is one or a combination of several of BYK-168 or polyethylene glycol.
8. The preparation method of the heat-insulating ultraviolet-shielding phase-change material according to claim 7, characterized by comprising the following steps: in the step (2), the cross-linking agent is one or a combination of more of trimethylolpropane triacrylate and UN-178; the photoinitiator is one or a combination of more of 2, 2-dimethyl acetophenone or diphenylethyl ketone.
9. The use of the insulating ultraviolet shielding phase-change material of claim 1 in the manufacture of an insulating ultraviolet shielding intelligent material.
10. Use according to claim 9, characterized in that: the heat-insulating ultraviolet shielding phase-change material is prepared into a coating material or a composite master batch material.
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| WO2018235833A1 (en) * | 2017-06-19 | 2018-12-27 | 住友金属鉱山株式会社 | Adhesive layer, near-infrared absorption film, laminated structure, laminate, adhesive composition, and method for producing same |
| CN111716833A (en) * | 2020-06-30 | 2020-09-29 | 江南大学 | Coating type multilayer transparent ultraviolet near-infrared shielding high polymer material, preparation method and application thereof |
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| CN114702850A (en) * | 2022-03-28 | 2022-07-05 | 湖北大学 | Vanadium dioxide composite powder temperature-control coating and preparation method thereof |
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| WO2018235833A1 (en) * | 2017-06-19 | 2018-12-27 | 住友金属鉱山株式会社 | Adhesive layer, near-infrared absorption film, laminated structure, laminate, adhesive composition, and method for producing same |
| CN111716833A (en) * | 2020-06-30 | 2020-09-29 | 江南大学 | Coating type multilayer transparent ultraviolet near-infrared shielding high polymer material, preparation method and application thereof |
| CN114057947A (en) * | 2021-10-22 | 2022-02-18 | 大连工业大学 | Bidirectional rapid photo-thermal response PVA-PNIPAM/MxWO3Composite hydrogel and preparation method thereof |
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