CN113667142A - Photo-thermal dual-response intelligent window and preparation method thereof - Google Patents
Photo-thermal dual-response intelligent window and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a photo-thermal dual-response intelligent window and a preparation method thereof. The intelligent window comprises a gel layer, wherein the gel layer comprises hydrogel formed by temperature-sensitive amide monomers and polydopamine-modified nanocellulose, and the mass percentage of the polydopamine to the temperature-sensitive amide monomers is 0.001% -0.02%. The intelligent window is prepared by taking amide hydrogel with temperature-sensitive property as a substrate and adding polydopamine modified nano-cellulose material with a photo-thermal conversion function. When the light intensity is larger or the room temperature is higher, the transparency is automatically changed into the non-transparency, and the natural light is scattered, so that the indoor light can not be dazzled but still bright, and meanwhile, the indoor temperature can also be maintained at a comfortable level for human bodies. And when the light intensity reduces and the temperature is lower, the intelligence window can resume to transparent state again for indoor temperature can keep relative stability, has the light and heat dual response nature.
Description
Technical Field
The application relates to the technical field of intelligent windows, in particular to a photo-thermal dual-response intelligent window and a preparation method thereof.
Background
With the increasing attention on environmental protection and energy conservation, the call for reasonable utilization of energy is getting bigger and bigger, and the development and development of energy-saving products are continuously making great progress. In this context, the research and application of "smart windows" has become a research hotspot. A Smart window (Smart window) is a device that can change optical properties such as transmittance of a window in response to external environmental stimuli, thereby adjusting the lighting effect and temperature of a room according to the sunlight taken into the room. Smart windows can be generally classified into three types: photochromic, electrochromic, and thermotropic. The principle of the photochromic intelligent window is that when a compound is irradiated by light with a specific wavelength, a product with different structures and spectral properties is generated through a specific chemical reaction, so that the transmittance is adjusted. Under the action of an external electric field, the electrochromic intelligent window enables the optical performance of the intelligent window material to be continuously and reversibly changed, and the color and the transparency of the intelligent window are reversibly changed. And the thermotropic light-adjusting intelligent window changes the transmission or absorption characteristics of the window to incident light rays depending on the change of the ambient temperature.
At present, most intelligent windows are liquid crystal intelligent windows, but liquid crystal materials are expensive, and the use conditions are complex, so that the application of the intelligent windows is greatly limited. In comparison, hydrogel materials (such as amide hydrogels) are low in cost, simple in use conditions, and good in performance in the aspect of optical switching characteristics. And the flexible hydrogel can be used for manufacturing a curved intelligent window, which cannot be realized by a liquid crystal intelligent window and the like. Therefore, hydrogel-based smart windows have become a major trend. However, the transparency of the current hydrogel intelligent window can be adjusted only by temperature, and the intelligent window loses the adjusting capability at low temperature and high light intensity, so that the current hydrogel intelligent window has certain use limitation.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the application provides an intelligent window with photo-thermal double response and a preparation method thereof.
In a first aspect of the application, an intelligent window is provided, which includes a gel layer, wherein the gel layer includes hydrogel formed by temperature-sensitive amide monomers and polydopamine-modified nanocellulose, and the mass percentage of polydopamine and temperature-sensitive amide monomers is 0.001% -0.02%.
According to the intelligent window of this application embodiment, have following beneficial effect at least:
the intelligent window is prepared by taking amide hydrogel with temperature-sensitive property as a substrate and adding polydopamine modified nano-cellulose material with a photo-thermal conversion function. The nano-cellulose has the advantages of large length-diameter ratio, good water dispersibility, large specific surface area and the like, is used as a reinforcing agent and a crosslinking agent in a hydrogel substrate, improves the durability of the intelligent window, and can effectively adjust the transition temperature of the intelligent window. And through the polydopamine of suitable content to the surface modification of nano-cellulose, bring the effect of absorbing the infrared light for intelligent window to obtain light and heat dual response ability, can effectively shield external infrared light, reduce indoor temperature, and be in colorless state when transparent, can not influence the normal use of intelligent window because of hindering light to see through the window. It can be seen that the intelligent window automatically changes from transparent to opaque when the light intensity is larger or the room temperature is higher, and scatters natural light, so that the indoor light can not be dazzled but still bright, and meanwhile, the indoor temperature can also be maintained at a comfortable level for a human body. And when the light intensity reduces and the temperature is lower, the intelligence window can resume to transparent state again for indoor temperature can keep relative stability, has the light and heat dual response nature.
In addition, the intelligent window that this application provided has extensive application, not only can be applied to the building, can also be used to on various vehicles, such as car, high-speed railway, aircraft etc.. At present, the method for reducing the light intensity of the automobile is realized by sticking a sun-proof film mostly, and because the transparency can not be freely regulated, the transmittance of visible light is too low when the illumination intensity is low, most of the visible light is reflected, the interior of the automobile is dim, and the phenomena of carsickness and the like of passengers are easily caused. While aircraft glass is currently mostly transparent glass, a few airlines use sun protection films. After the aircraft rises to on the cloud layer, illumination intensity becomes stronger, and is bigger to the injury of skin and eyes, and the intelligent window that sampling this application provided can in time protect the passenger to avoid the influence of highlight. The temperature-sensitive amide hydrogel added with the nano-cellulose has a three-dimensional network structure, has good mechanical properties, can absorb external acting forces such as airflow impact and the like to a certain extent, and has good use reliability and long service life.
In some embodiments of the present application, the mass percentage of polydopamine to the temperature-sensitive amide monomer is 0.001% to 0.013%.
In some embodiments of isopropylacrylamide of the present application, the temperature-sensitive amide monomer is isopropylacrylamide.
In some embodiments of the present application, the mass ratio of polydopamine to nanocellulose is 1: (3-8).
In some embodiments of the present application, the nanocellulose is selected from at least one of cellulose nanocrystals, cellulose nanofibers, bacterial nanocellulose.
In some embodiments of the present application, 1200W/m when the temperature reaches above 32 deg.C2When at least one of the above illumination occurs, the smart window becomes opaque; when the temperature is lower than 32 ℃ and the strong light irradiation disappears, the intelligent window becomes transparent.
In a second aspect of the present application, there is provided a method of manufacturing a smart window, the method comprising the steps of:
step 1: taking the dispersion liquid of the nano-cellulose, adjusting the pH value to 8-9, and mixing the dispersion liquid with dopamine for reaction for 12-48 h to obtain a dispersion liquid of the polydopamine modified nano-cellulose;
step 2: and mixing the dispersion liquid of the polydopamine-modified nano-cellulose with a temperature-sensitive amide monomer, an initiator and a cross-linking agent to form a reaction system, and reacting to obtain the intelligent window.
In some embodiments of the present application, the dispersion of nanocellulose is prepared by a method comprising: mixing cellulose with acid liquor, and hydrolyzing to obtain dispersion of nano cellulose.
In some embodiments of the present application, the acid used to hydrolyze the cellulose is concentrated sulfuric acid.
In some embodiments herein, after the reaction is complete, the reaction is terminated by dilution with water.
In some embodiments of the present application, the ratio of cellulose to concentrated sulfuric acid is (15-30) g: (150-300) mL.
In some embodiments of the present application, the temperature of the hydrolysis reaction is 30 to 70 ℃, and the time of the hydrolysis reaction is 1 to 2 hours.
In some embodiments of the present application, the hydrolyzed nanocellulose is obtained by centrifugation, washing, and the like, followed by dialysis.
In some embodiments of the present application, the cellulose is at least one of pulp cellulose, microcrystalline cellulose, and bacterial cellulose.
In some embodiments of the present application, the reaction conditions of nanocellulose and dopamine are atmospheric environment, i.e. the reaction raw materials can be contacted with air under non-airtight conditions.
In some embodiments herein, the initiator is selected from at least one of peroxide initiators, azo initiators. Non-limiting examples of peroxide initiators include cyclohexanone peroxide, dibenzoyl peroxide, t-butyl hydroperoxide, etc., and non-limiting examples of azo initiators include azobisisobutyronitrile, azobisisoheptonitrile, etc.
In some embodiments of the present application, the method of forming the smart window is transferring the reaction system into a mold for standing reaction.
In some embodiments of the present application, the pH of the nanocellulose dispersion was adjusted to 8.5 using 0.01mol/L sodium hydroxide.
In some embodiments of the present application, tris was used as a buffer pair to maintain the pH of the nanocellulose dispersion stable at 8.5 during the reaction.
In some embodiments herein, the initiator is ammonium persulfate.
In some embodiments herein, the catalyst is tetramethylethylenediamine.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
Fig. 1 is a schematic structural view of a photothermal dual-responsive smart window in one embodiment of the present application.
Fig. 2 is an infrared spectrum of nanocellulose and polydopamine-nanocellulose in one example of the present application.
FIG. 3 is a graph of the absorption spectrum of a photothermal dual-response smart window at 300nm-1700nm in one embodiment of the present application.
FIG. 4 is a graph of the transmission spectrum of a photothermal dual response smart window at 300nm to 1700nm in one embodiment of the present application.
Fig. 5 is a photograph of a photothermal dual response smart window in a transparent state and an opaque state in one embodiment of the present application.
Fig. 6 is a photograph of the polydopamine hydrogel prepared in the comparative example of the present application.
Reference numerals: a first glass layer 110, a second glass layer 120, a gel layer 130.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for the purpose of illustration only and is not intended to be construed as a limitation of the application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, unless otherwise expressly limited, terms such as set, mounted, connected and the like should be construed broadly, and those skilled in the art can reasonably determine the specific meaning of the terms in the present application by combining the detailed contents of the technical solutions.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The present embodiment provides a photo-thermal dual-response smart window, and referring to fig. 1, the smart window includes a mold formed by a first glass layer 110 and a second glass layer 120, and a gel layer 130 disposed between the first glass layer 110 and the second glass layer 120, wherein the gel layer 130 is obtained by reacting raw materials including isopropyl acrylamide, dopamine, nanocellulose, initiator, crosslinking agent, catalyst, and the like.
The preparation method of the intelligent window comprises the following steps:
(1) preparation of a Nanocellulose suspension
Adding 15g of microcrystalline cellulose into 300mL of concentrated sulfuric acid, heating and stirring for acidolysis, and adding deionized water with the volume 10 times that of the concentrated sulfuric acid to terminate the reaction, thereby obtaining a suspension of the nanocellulose. Centrifuging the suspension, removing supernatant, centrifuging and washing the lower layer precipitate for multiple times, dialyzing for several days after ultrasonic treatment, finally performing ultrasonic treatment again to obtain nano-cellulose dispersion, and placing the nano-cellulose dispersion in a cold storage layer of a refrigerator for later use.
(2) Preparation of polydopamine modified nanocellulose
The concentration of the dispersion of the nanocellulose in (1) was adjusted to 0.5 wt%, followed by the addition of 0.01mol/L sodium hydroxide to adjust the pH to 8.5, and the addition of tris (hydroxymethyl) aminomethane as a buffer pair to stabilize the pH of the dispersion at 8.5 during the reaction. And then, according to the mass ratio of the nano-cellulose to the dopamine of 5: 1 adding dopamine, and reacting for 24 hours at room temperature in the atmospheric environment to obtain the dispersion liquid of the polydopamine modified nano-cellulose.
(3) Preparation of smart windows
Preparing an aqueous solution of isopropyl acrylamide with the mass concentration of 20%, wherein the volume ratio of the aqueous solution of isopropyl acrylamide to the dispersion liquid of the polydopamine modified nano-cellulose is 45: 1 mixing the two, and stirring uniformly. Then, according to the mass ratio of the methylene bisacrylamide to the isopropyl acrylamide of 1: 100, adding methylene bisacrylamide (a cross-linking agent), wherein the mass ratio of ammonium persulfate to isopropyl acrylamide is 7: 4000, adding ammonium persulfate (initiator) according to the volume ratio of the tetramethylethylenediamine to the isopropylacrylamide solution of 1: 100 adding tetramethyl ethylenediamine (catalyst) to obtain a hydrogel reaction system. And (3) after the reaction system is uniformly stirred, pouring the mixture into a hollow mould formed by the first glass layer and the second glass layer, and standing for 24 hours to obtain the photo-thermal dual-response intelligent window.
FIG. 2 is an infrared spectrum of the nanocellulose (CNC) and polydopamine modified nanocellulose (PDA @ CNC) during the preparation process, from which it can be seen that PDA @ CNC is 1510cm-1A new characteristic peak appears, mainly comes from the N-H bond of polydopamine, and shows that polydopamine is successfully grafted on the nano-cellulose, and the polydopamine modified nano-cellulose is successfully prepared. .
Example 2
This example provides a photothermal dual-response smart window, which differs from example 1 only in that the volume ratio of the isopropylacrylamide solution to the polydopamine-modified nanocellulose dispersion is 45: and 2, obtaining an intelligent window with the mass percentage of the polydopamine modified nano-cellulose in the hydrogel being 1%.
Example 3
This example provides a photothermal dual-response smart window, which differs from example 1 only in that the volume ratio of the isopropylacrylamide solution to the polydopamine-modified nanocellulose dispersion is 45: and 4, obtaining an intelligent window with the polydopamine modified nano-cellulose mass percent of 2% in the hydrogel.
Example 4
This example provides a photothermal dual-response smart window, which differs from example 1 only in that the volume ratio of the isopropylacrylamide solution to the polydopamine-modified nanocellulose dispersion is 45: and 8, obtaining an intelligent window with the polydopamine modified nano-cellulose mass percent of 4% in the hydrogel.
Example 5
This example provides a photothermal dual-response smart window, which differs from example 1 only in that the volume ratio of the isopropylacrylamide solution to the polydopamine-modified nanocellulose dispersion is 45: 12, obtaining an intelligent window with the mass percentage of 6% of polydopamine modified nano-cellulose in the hydrogel.
Spectrum detection experiment
And (3) respectively taking the intelligent windows prepared in the examples 2-4 and the comparative example 1, and detecting the absorption spectrum and the transmission spectrum of the intelligent windows. Comparative example 1 differs from example 1 in that the polydopamine modification of step (2) is not included.
The results are shown in fig. 3 and 4, respectively. Referring to fig. 3, which is an absorption spectrum diagram, the peak positions at 1400nm to 1600nm are, from high to low, example 4, example 3, example 2 and comparative example 1, respectively, and it can be seen from the diagram that as the concentration of polydopamine modified nanocellulose in the smart window is increased, the absorbance is increased, and the absorption in the near infrared band is enhanced, while there is a clear difference in comparison with example 1 in comparison with examples 2 to 4. Referring to fig. 4, which is a transmission spectrum diagram, the transmission spectrum is shown from top to bottom for comparative example 1, example 2, example 3 and example 4, respectively, and it can be seen from the diagram that as the concentration of polydopamine modified nanocellulose in the smart window increases, the light transmittance decreases, and the absorption in the near infrared band increases, whereas the light transmittance of comparative example 1 is the highest in the band compared with examples 2 to 4.
Photo-thermal double response experiment
The smart window prepared in example 1 was transparent as shown in B) of fig. 5 when left at room temperature; the smart window is placed in the palm of the hand for 15min, or irradiated by near infrared light, as shown in A) of FIG. 5, and then turned into an opaque state. And after the temperature is balanced to the room temperature or the near infrared light is turned off, the transparent state is converted again.
Comparative experiment of preparation method
Comparative example 2
The comparative example provides a hydrogel material, which was prepared as follows:
(1) preparation of Polydopamine suspensions
Taking 200mL of 33 vol% ethanol aqueous solution, adding a small amount of ammonia water, stirring for 10 minutes, then adding 1g of dopamine polyhydrochloride, stirring and reacting for 24 hours at room temperature under an atmospheric environment, carrying out ultrasonic treatment on reaction liquid after the reaction is finished, dialyzing for several days, finally carrying out ultrasonic treatment again to obtain a polydopamine suspension, and placing the polydopamine suspension in a refrigerator cold storage layer for later use.
(2) Preparation of hydrogels
Adding 3g of 2-methyl-2-acrylic acid-2 (2-methoxyethoxy) ethyl ester, the suspension containing 9g of polydopamine nanoparticles in the step (1), 1g of nano-cellulose suspension and 2mg of methylene bisacrylamide serving as a cross-linking agent into a reaction tube, reacting for 10 minutes, adding a proper amount of ammonium persulfate and tetramethyl diethylamine, sealing the reaction tube in an anaerobic manner, and standing at 10 ℃ for 12 hours to obtain the hydrogel.
As shown in FIG. 6, the hydrogel is a black opaque hydrogel, and cannot be used as an intelligent window compared with examples 1 to 5.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
Claims (10)
1. The intelligent window is characterized by comprising a gel layer, wherein the gel layer comprises hydrogel formed by temperature-sensitive amide monomers and polydopamine-modified nanocellulose, and the mass percentage of the polydopamine to the temperature-sensitive amide monomers is 0.001% -0.02%.
2. The smart window of claim 1, wherein the temperature sensitive amide monomer is isopropyl acrylamide.
3. The smart window of claim 1, wherein the mass ratio of polydopamine to nanocellulose is 1: (3-8).
4. The smart window according to any one of claims 1 to 3, wherein the nanocellulose is selected from at least one of cellulose nanocrystals, cellulose nanofibers, bacterial nanocellulose.
5. The smart window of any one of claims 1 to 3, wherein 1200W/m when the temperature reaches above 32 ℃2Upon at least one of the above illuminations, the smart window becomes opaque; when the temperature is lower than 32 ℃ and the strong light irradiation disappears, the intelligent window becomes transparent.
6. The method of manufacturing a smart window according to any one of claims 1 to 5, comprising the steps of:
step 1: taking the dispersion liquid of the nano-cellulose, adjusting the pH value to 8-9, and mixing the dispersion liquid with dopamine for reaction for 12-48 h to obtain a dispersion liquid of the polydopamine modified nano-cellulose;
step 2: and mixing the dispersion liquid of the polydopamine-modified nano-cellulose with a temperature-sensitive amide monomer, an initiator and a cross-linking agent to form a reaction system, and reacting to obtain the intelligent window.
7. The method according to claim 6, wherein the dispersion of nanocellulose is prepared by: mixing cellulose with acid liquor, and hydrolyzing to obtain dispersion of nano cellulose.
8. The method according to claim 7, wherein the cellulose is at least one of pulp cellulose, microcrystalline cellulose, and bacterial cellulose.
9. The method according to any one of claims 6 to 8, wherein the initiator is at least one selected from a peroxide initiator and an azo initiator.
10. The method for preparing according to any one of claims 6 to 8, wherein the method for forming the smart window is transferring the reaction system into a mold for standing reaction.
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| CN115367829A (en) * | 2022-07-20 | 2022-11-22 | 成都理工大学 | Treatment method of Janus structure hydrogel for desalting and pollution reducing of fracturing flow-back fluid |
| CN115367829B (en) * | 2022-07-20 | 2023-09-15 | 成都理工大学 | Treatment method for desalting and pollution reduction of fracturing flowback fluid by using Janus structure hydrogel |
| CN115503307A (en) * | 2022-10-18 | 2022-12-23 | 上海骊港幕墙科技有限公司 | Photo-thermal dual-response intelligent window and preparation method thereof |
| CN115838485A (en) * | 2023-02-21 | 2023-03-24 | 广东工业大学 | Temperature self-adaptive hydrogel intelligent window based on modified polyvinyl alcohol gel material |
| CN115838485B (en) * | 2023-02-21 | 2023-10-24 | 广东工业大学 | Temperature self-adaptive hydrogel intelligent window based on modified polyvinyl alcohol gel material |
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