CN116836437B - Preparation method and application of temperature and humidity regulation film based on porous polymer layer/photo-thermal layer - Google Patents
Preparation method and application of temperature and humidity regulation film based on porous polymer layer/photo-thermal layer Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 46
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 26
- 230000005855 radiation Effects 0.000 abstract description 25
- 238000001816 cooling Methods 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 229920000128 polypyrrole Polymers 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 238000002310 reflectometry Methods 0.000 description 5
- 238000007791 dehumidification Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
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- 238000012512 characterization method Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
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- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/10—Esters of organic acids
- C08J2401/12—Cellulose acetate
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Abstract
The invention discloses a preparation method and application of a temperature and humidity regulation film based on a porous polymer layer/photo-thermal layer. According to the method, a porous cellulose acetate film with a proper aperture is covered on the surface of a PPy photo-thermal film for the first time by a phase conversion method, and then the humidity-driven temperature and humidity regulation film with a multilayer structure is prepared. The proper pore diameter is designed to be beneficial to improving the scattering effect of the upper cellulose acetate film on solar radiation in a dry state, and the combination of the low intrinsic absorption property of the cellulose acetate on the solar radiation ensures that the solar reflectance of the film in the dry state is more than 80 percent. After the film is applied with the hygroscopic salt solution, the photo-thermal and radiation cooling effects of the film can be reversibly and autonomously switched through internal humidity adjustment, so that the temperature and humidity can be regulated and controlled. The multilayer film structure constructed by the design can be used as a humidity-driven temperature and humidity regulator for regulating and controlling the temperature and the humidity of the enclosed space.
Description
Technical Field
The invention relates to the field of radiation refrigeration and photo-thermal conversion, in particular to a preparation method and application of a temperature and humidity regulation film based on a porous polymer layer/photo-thermal layer.
Background
Indoor environmental control is becoming indispensable in modern life of people. At present, most of heating, refrigerating, dehumidifying and other tasks need to be completed through an air conditioner, an electric heater, an electric humidifier, a dehumidifier and the like. Such electric energy driven home devices are accompanied by a large amount of energy consumption and emission of greenhouse gases. Second, the above devices are also not suitable for use in remote areas where resources are barren due to their expensive equipment purchase price, complex installation and large power consumption.
Compared with electric energy driving, the indoor environment regulation driven by clean energy has a profound development prospect. The solar radiation is a clean energy which is easy to obtain and widely distributed. The absorbed light energy can be converted into heat without emission by means of a photo-thermal material. In contrast to solar photothermal technology, daytime radiation cooling technology is to block incident solar radiation by strong scattering effect in solar spectrum range, and radiate the loaded heat to the external space through an atmospheric window (8-13 μm) by utilizing the high emissivity of the material, so as to achieve the purpose of radiation cooling. The two strategies respectively realize the heating and cooling functions driven by clean energy. The photothermal technology requires that the designed material has high absorptivity in the solar spectrum. Whereas daytime radiation cooling strategies require materials designed to have high reflectivity in the solar wavelength and high emissivity in the mid-infrared, especially atmospheric window spectral range. However, the designed single spectrum material cannot meet the two requirements at the same time, and is difficult to adapt to seasonal temperature fluctuation, so that a material with dynamic sunlight scattering needs to be developed to realize a reversible photo-thermal/radiation cooling function.
Disclosure of Invention
The invention provides a preparation method of a temperature and humidity regulation film based on a porous polymer layer/photo-thermal layer.
The invention realizes high reflectivity in the solar spectrum range by utilizing the large refractive index difference between the main body of the polymer network and the air in the pores in the dry state, and realizes high emissivity of the atmospheric window by utilizing the telescopic vibration of a large number of C-O groups in the cellulose acetate polymer, thereby realizing the radiation cooling effect. The pore air is replaced by water with a high refractive index value when the film is in a wet state, so that the reflectivity of the material is reduced, sunlight is guided to be absorbed by a lower photo-thermal film, and the conversion from radiation cooling to photo-thermal effect is realized. The film can realize reversible switching between cooling and heating states through self-deliquescence and photo-thermal evaporation of hygroscopic salt. The multilayer structure film prepared by the technology can be used as a closed environment, and temperature and humidity regulation without additional energy driving is provided.
The preparation method of the temperature and humidity regulation film based on the porous polymer layer/photo-thermal layer is characterized by comprising the following steps of:
1) Dispersing pyrrole monomer in water, and performing ultrasonic dispersion to obtain a solution A;
Adding FeCl 3 and hydrochloric acid into water, and uniformly mixing to obtain a solution B;
And rapidly mixing the solution A and the solution B, placing filter paper in the mixed solution, enabling Fe 3+ to serve as a chemical oxidant in the solution to guide pyrrole monomers to polymerize and attach on the surface of the filter paper, regulating the pH value of the solution to maintain an acidic environment by hydrochloric acid, ensuring the polymerization of pyrrole, and maintaining the ionic state of iron. Then cleaning the filter paper fully attached with polypyrrole with alcohol and deionized water in sequence, and drying to obtain a PPy photo-thermal film;
2) Ethanol and acetone were mixed as a solvent, and then cellulose acetate powder was added thereto to form a colorless transparent mixed solution. In this solution, acetone acts as a benign solvent for cellulose acetate, and ethanol acts as a non-benign solvent component. CaCl 2 is then dispersed in the mixed solvent to increase the hydrophilicity of the subsequently obtained cellulose acetate film and impart self-moisture absorption properties. Heating the mixed solution at 20-40 ℃ for 10-30 mins to uniformly mix all the components to obtain a precursor solution, then completely immersing the PPy photo-thermal film prepared in the step 1) into the precursor solution for 5mins, taking out and naturally airing, wherein in the airing process, a benign solvent acetone with a lower boiling point is volatilized firstly to gradually precipitate cellulose acetate, and then, the volatilization of a non-benign solvent ethanol is carried out to leave a porous structure on the surface of the film. The separated porous cellulose acetate film is closely adhered to the surface of the PPy photo-thermal film, so that a porous cellulose acetate/PPy photo-thermal layer multilayer film is obtained;
3) Dissolving CaCl 2 in water to obtain a hygroscopic salt solution; and then immersing the porous cellulose acetate/PPy photo-thermal layer multilayer film obtained in the step 2) into a hygroscopic salt solution, wherein the CaCl 2 solution with higher concentration can improve the self-hygroscopic property of the film, and drying after taking out to obtain the high-hygroscopic porous cellulose acetate/PPy photo-thermal layer multilayer film.
The method prepares the porous cellulose acetate film with proper aperture by a phase conversion method for the first time, and prepares the humidity-driven temperature and humidity regulation film with a multilayer structure after the porous cellulose acetate film is compounded with the PPy photo-thermal film. The proper pore diameter is designed to be beneficial to improving the scattering effect of the cellulose acetate film on solar radiation in a dry state, and the combination of the low intrinsic absorption property of the cellulose acetate on the solar radiation ensures that the solar reflectance of the film in the dry state is more than 80 percent. In addition, the large amount of C-O groups contained in the cellulose acetate structure is utilized to enable the cellulose acetate structure to reach higher emissivity (> 0.8) in the atmospheric window spectrum range (8-13 μm), so that the radiation cooling performance in a dry state is obtained. When the air (n=1.03) inside the pores inside the porous cellulose film is replaced by water (n=1.33) which is closer to the refractive index (n=1.47) of the cellulose, the scattering effect of the cellulose acetate film on the sunlight is weakened, and the received solar radiation is guided to pass through the upper porous cellulose acetate layer, so that the solar radiation is absorbed by the lower photo-thermal material layer, and the sunlight heating effect is achieved. After the film is applied with the hygroscopic salt solution, the photo-thermal and radiation cooling effects of the film can be reversibly and autonomously switched through internal humidity adjustment, so that the temperature and humidity can be regulated and controlled. The multilayer film structure constructed by the design can be used as a humidity-driven temperature and humidity regulator for regulating and controlling the temperature and the humidity of the enclosed space.
In step 1), the solution A is prepared by the following steps of: 20 to 80mL (more preferably 40 to 60 mL) of pyrrole monomer and water;
The dosage ratio of the solution B is 5-9 g:0.5 to 2mL (more preferably, 6.8g:1.25 mL) of FeCl 3 and hydrochloric acid;
The mass percentage of the hydrochloric acid is 35-38%, and more preferably 37%.
And the cleaning is carried out after the mixture is kept stand for 0.5 to 3 hours at the temperature of 10 to 35 ℃, and more preferably, the cleaning is carried out after the mixture is kept stand for 1 hour at the temperature of 25 ℃.
In the step 2), the dosage ratio of the ethanol, the acetone, the cellulose acetate powder and the CaCl 2 is 8-12 mL: 8-12 mL:1.0g:0.8 to 1.2g, more preferably 10mL:10mL:1.0g:1.0g.
Heating at 25-45 deg.c for 15-25 min, and preferably at 30 deg.c for 20 min.
In the step 2), the PPy photo-thermal film prepared in the step 1) is immersed in the precursor solution for 0.5 to 5 minutes, and more preferably, the PPy photo-thermal film prepared in the step 1) is immersed in the precursor solution for 1 minute.
In step 3), the porous cellulose acetate/PPy photo-thermal layer multilayer film obtained in step 2) is immersed in a hygroscopic salt solution for 0.5 to 2 hours, and more preferably for 1 hour.
The hygroscopic salt solution is formed by mixing CaCl 2 and water, and the dosage ratio of CaCl 2 to water is 1-3 g:5 to 15mL, more preferably 2g:10mL.
The concentration of the hygroscopic salt solution is 14 to 19wt%, and more preferably 16.67wt%.
The temperature and humidity regulation film based on the porous polymer layer/photo-thermal layer prepared by the preparation method is applied to temperature and humidity regulation.
Most preferably, the humidity driving method can be used for preparing a temperature and humidity regulating film, preparing a porous cellulose acetate/PPy photo-thermal film multilayer film and preparing a humidity control temperature and humidity reversible switching behavior of the film, and comprises the following steps of:
1) Preparing a PPy photo-thermal film: 100 μl of pyrrole monomer solution was dispersed in 50mL deionized water, and sonicated for 10 minutes to give solution a. To deionized water, 6.8g FeCl 3 and 37.0% HCl (1.25 mL) were added and mixed to give solution B. And then quickly mixing the solutions A and B, immersing filter paper into the mixed solution to serve as a matrix for attaching polypyrrole, carrying out polymerization reaction for 1 hour at the room temperature of 25 ℃, taking out the filter paper growing with the polypyrrole, sequentially cleaning the filter paper by using ethanol and deionized water, and drying at the room temperature to obtain the PPy photo-thermal film.
2) Preparing the porous cellulose acetate/PPy photo-thermal layer multilayer film. Mixing ethanol and acetone in different volume ratios to obtain a mixed solvent, adding cellulose acetate powder to form a mixed solution, dispersing hygroscopic salt into the mixed solvent, and heating at 30 ℃ for 20min to obtain a precursor solution. And then immersing the photo-thermal film prepared in the step 1) into a precursor solution, and obtaining a porous cellulose acetate layer with different porosities by utilizing different volatilization rates of a solvent and a non-solvent, wherein the cellulose acetate layer is closely adhered to the surface of the PPy photo-thermal layer, so that the porous cellulose acetate layer/PPy photo-thermal layer multilayer film is obtained.
In step 2), the ratio of ethanol to acetone was 0:10mL,2.5:10mL,5:10mL,7.5:10mL,10:10mL, respectively.
It is further preferred that the volume ratio of ethanol to acetone be 10:10mL.
3) Preparing a high-hygroscopicity porous cellulose acetate/PPy photo-thermal layer multilayer film. And dissolving the hygroscopic salt powder in deionized water to obtain a hygroscopic salt solution. Thereafter, the multilayer film obtained in step 2) was immersed in a hygroscopic salt solution for 1 hour. The obtained high hygroscopicity multilayer film is dried under natural condition and stored for standby.
The hygroscopic salt powder is selected as CaCl 2, and the mass is 2g.
The deionized water solution is 10mL.
The multilayer structure film prepared above can be used as a regulator of a closed environment, and clean temperature and humidity regulation is provided.
Compared with the prior art, the invention has the following outstanding characteristics and beneficial effects:
(1) The invention utilizes the large refractive index difference ((delta n=n CA-nair =1.47-1.00=0.47) between air in the pores and the cellulose acetate main body in the dry state to realize high reflectivity (0.87) in the solar spectrum range, and utilizes the C-O groups rich in cellulose acetate molecules to realize high emissivity (0.85) of middle infrared, thereby realizing daytime radiation cooling effect.
(2) The invention utilizes the smaller refractive index difference value (delta n=n CA-nwater =1.47-1.33=0.14) between the water in the pores and the cellulose acetate main body in the wet state to realize high absorptivity (0.95) in the solar spectrum range, thereby realizing the high-efficiency photo-thermal effect.
(3) The photo-thermal effect and the radiation cooling effect can be reversibly switched by photo-thermal evaporation and water wetting, which are not possessed by other temperature regulating films with single functions.
(4) The obtained temperature and humidity regulation film is subjected to moisture absorption salt solution (16.7 wt%) treatment, so that excellent moisture absorption performance is provided for the film, the obtained film can realize the photo-thermal dehumidification effect of a closed space under the photo-thermal effect, and the film can be driven to spontaneously change from a dry state to a wet state under higher humidity.
Drawings
FIG. 1 is a diagram showing the preparation process and structural characterization of a temperature control film. FIG. a is a schematic diagram of a film preparation process. Figure b is a photograph of the appearance of the film in dry form. Figure c is a scanning electron microscope picture of the upper acetate fiber layer, with the inset showing the internal pore size distribution. And the figure d is a side sectional view of the temperature regulating film, wherein the upper layer is porous cellulose acetate, and the lower layer is a PPy photo-thermal film.
FIG. 2 is a graph of temperature controlled film spectra under different wet conditions. The figure a comprises an appearance diagram of a photo-thermal regulation film in a dry state and a wet state, the figure b is a schematic diagram of interaction between films in different wet states and solar radiation, and the figure c is a spectrogram of the temperature regulation film in different wet states.
Fig. 3 shows the switching effect of the photo-thermal control film in different states by humidity. Fig. a is a schematic diagram of state switching and a photo diagram, and fig. b is a schematic diagram of heating and cooling of a closed space by films in different wetting states. Figure c is an infrared picture of different wet state films on a model house.
FIG. 4 shows the photo-thermal dehumidification of an enclosed space by a temperature control film after application of a hygroscopic salt solution. Figure a shows the humidity variation of the enclosure at different stages. Figure b is a schematic diagram of a dehumidification application.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Example 1
A preparation method of a temperature and humidity regulation film based on a porous polymer layer/photo-thermal layer comprises the following steps:
1. The preparation process of the method
100. Mu.L of pyrrole monomer solution was dispersed in 50mL of deionized water, and the dispersion was performed for 10 minutes to obtain pyrrole monomer solution. Another 50mL of deionized water was added thereto, and 6.8g of FeCl 3 and 37.0% HCl (1.25 mL) were mixed to obtain an oxidizing agent solution. And then rapidly mixing the pyrrole monomer solution and the oxidant solution, placing filter paper in the mixed solution, keeping the mixed solution at the room temperature of 25 ℃ for 1 hour, sequentially cleaning the filter paper attached to the PPy by using ethanol and deionized water, and drying the filter paper at the room temperature of 25 ℃ to obtain the PPy photo-thermal film. Ethanol and acetone were mixed at 1:1 to obtain 20mL of a mixed solvent as a phase-transfer solution, then adding 1g of cellulose acetate powder to the mixed solvent to obtain a mixed solution, then dispersing 1gCaCl 2 into the mixed solution, and heating at 30 ℃ for 20 minutes to obtain a precursor solution. And then immersing the prepared PPy photo-thermal film into the precursor solution for 1min, taking out, and naturally airing for 5min to cover the surface of the PPy photo-thermal film with porous cellulose acetate, thereby obtaining the temperature regulation film. To impart moisture absorption to the temperature-controlled film, 2g of CaCl 2 powder was dissolved in 10mL of deionized water to give a moisture absorbing salt solution. Then, the temperature-controlled film prepared previously was immersed in a hygroscopic salt solution for 1 hour. The obtained high hygroscopicity multilayer film is dried under natural condition and stored for standby.
2. The treatment process of the method of the invention
(1) Placing the prepared temperature regulation film into a scanning electron microscope, observing the microscopic morphological characteristics of the porous cellulose acetate covered on the upper layer, counting the average pore size, and observing the sectional view of the prepared film to verify the multilayer structure of the film.
(2) And recording the absorption rate of the film in different wavelengths in the solar spectrum range by using a UV-Vis-NEAR INFRARED spectrophotometer with an integrating sphere under the dry state and the wet state of the prepared film. The prepared film was tested for emissivity at mid-infrared wavelengths using an infrared spectrometer with an integrating sphere.
(3) And packaging the prepared film by polyethylene, and switching the photo-thermal/radiation cooling effect by wetting and evaporating. The film was placed on the surface of a polystyrene-encapsulated cavity and its effect on the temperature in the cavity was measured.
(4) The film after moisture absorption salt treatment was placed on the surface of a cavity encapsulated with polystyrene, and its effect on the humidity and temperature in the cavity was measured.
3. The effects obtained by this example of the invention
This example demonstrates that the upper cellulose acetate layer in the dry state has a high scattering effect on solar radiation, and that the scattering effect is reduced in the wet state, and that the transmitted solar radiation can be absorbed by the lower film layer to produce a photothermal effect. The prepared multilayer film can realize the temperature regulation and control of the sealed space, and the film applying the hygroscopic salt solution can realize the photo-thermal dehumidification effect of the sealed space.
FIG. 1 is a diagram showing the preparation process and structural characterization of a temperature control film. Fig. a is a schematic diagram of a preparation process of a multilayer temperature regulation film, wherein cellulose acetate is precipitated on the surface of a PPy photo-thermal film in a porous form by a phase conversion method, so that the cellulose acetate is wrapped on the outer side. Figure b is a digital photograph of a dry film, which demonstrates a strong scattering effect in the visible range. And the graph c is a scanning electron microscope image of the upper layer cellulose acetate, and proves that the cellulose acetate film separated by phase conversion has a porous structure, and the pore size is concentrated and distributed at 2 microns. The cross-sectional scanning electron microscope image demonstrates that the prepared film has a multi-layer structure.
FIG. 2 is a digital photograph and a spectrum of a multilayer film in different wet states, and FIG. a is a digital photograph showing the difference appearance of a unified multilayer film in different wet states, wherein the dry state part is white and the wet state part is black. Figure b is a schematic illustration of the interaction of different wet and dry films with incident sunlight. Figure c is a spectral plot of the multilayer film in the dry as well as in the wet state. The multilayer film has a higher light absorption in the solar spectral range (0.95) in the wet state, and a higher reflectivity in the dry state (0.87) while having a high emissivity in the mid-infrared range (0.85).
As shown in fig. 3, the multilayer film is sealed vm by transparent polyethylene, can be reversibly switched between a photo-thermal state and a radiation cooling state by wetting and evaporating, and can raise the temperature of an 80cm3 sealed space to 12 ℃ in a wet state and lower the temperature to 8 ℃ in a dry state.
Fig. 4 shows a prepared multi-layer film after application of hygroscopic salt, the humidity of the sealed space is slightly reduced under dark condition, the liquid water absorbed by the multi-layer film is rapidly discharged along with the introduction of illumination, the humidity of the sealed space is further reduced to 60% RH, and the film is switched from a wet state to a dry state to reduce the heating effect on the room.
Claims (8)
1. The preparation method of the temperature and humidity regulation film based on the porous polymer layer/photo-thermal layer is characterized by comprising the following steps of:
1) Dispersing pyrrole monomer in water, and performing ultrasonic dispersion to obtain a solution A;
Adding FeCl 3 and hydrochloric acid into water, and uniformly mixing to obtain a solution B;
Rapidly mixing the solution A and the solution B, placing common filter paper into the mixed solution, standing, cleaning, and drying to obtain a PPy photo-thermal film;
2) Mixing ethanol and acetone to prepare a mixed solvent, adding cellulose acetate powder into the mixed solvent to obtain a solution C, dispersing CaCl 2 into the solution C, heating at 20-40 ℃, completely immersing the PPy photo-thermal film prepared in the step 1) in the solution C, taking out, and naturally airing to obtain a multi-layer film with a porous cellulose acetate film uniformly wrapped by the PPy photo-thermal layer;
the ratio of the dosage of the ethanol, the acetone, the cellulose acetate powder and the CaCl 2 is 8-12 mL: 8-12 mL:1 g: 0.8-1.2 g;
3) Dissolving CaCl 2 in water to obtain a hygroscopic salt solution D; and then immersing the multilayer film obtained in the step 2) into the solution D, taking out and drying to obtain the porous cellulose acetate layer/PPy photo-thermal layer multilayer film with high moisture absorption performance.
2. The method for preparing a temperature and humidity control film based on a porous polymer layer/photo-thermal layer according to claim 1, wherein in the step 1), the solution a is prepared by a volume ratio of 100 μl: 20-80 mL of pyrrole monomer and water are mixed;
the dosage ratio of the solution B is 5-9 g: 0.5-2 mL of FeCl 3 and hydrochloric acid.
3. The method for preparing the temperature and humidity control film based on the porous polymer layer/the photo-thermal layer according to claim 1, wherein in the step 1), the film is cleaned after being kept stand at 10-35 ℃ for 0.5-3 hours.
4. The preparation method of the temperature and humidity control film based on the porous polymer layer/photo-thermal layer according to claim 1, wherein in the step 2), the film is heated for 15-25 min at 25-35 ℃.
5. The method for preparing the temperature and humidity control film based on the porous polymer layer/photo-thermal layer according to claim 1, wherein in the step 2), the PPy photo-thermal film prepared in the step 1) is immersed in a solution C0.5-5 min.
6. The preparation method of the temperature and humidity control film based on the porous polymer layer/photo-thermal layer according to claim 1, wherein in the step 3), the porous cellulose acetate/PPy photo-thermal layer multilayer film obtained in the step 2) is immersed in a hygroscopic salt solution D for 0.5-2 hours.
7. The preparation method of the temperature and humidity regulation film based on the porous polymer layer/photo-thermal layer according to claim 1, wherein in the step 3), the hygroscopic salt solution D is formed by mixing CaCl 2 and water, and the dosage ratio of CaCl 2 to water is 1-3 g: 5-15 mL.
8. The application of the temperature and humidity regulation film based on the porous polymer layer/photo-thermal layer prepared by the preparation method according to any one of claims 1-7 in temperature and humidity regulation.
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