CN116769085A - Preparation of intelligent window middle interlayer hydrogel with solar spectrum modulation - Google Patents
Preparation of intelligent window middle interlayer hydrogel with solar spectrum modulation Download PDFInfo
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Abstract
The application discloses preparation of intelligent window middle interlayer hydrogel with solar spectrum modulation, and belongs to the technical field of gel materials. According to the application, the polyvinyl alcohol is grafted and modified by using an aldehyde compound, the obtained product is placed in a saturated sodium bicarbonate solution for termination reaction, the precipitated white solid is subjected to impurity removal, and vacuum freeze drying to obtain white particles, namely a modified polyvinyl alcohol material; dissolving the modified polyvinyl alcohol material, performing ultrasonic treatment, removing bubbles, centrifuging, pouring, then placing in a closed saturated lithium chloride salt solution environment to evaporate a solvent, completely taking out bubble water after the solvent evaporates, obtaining a transparent hydrophobic association phase change gel material formed by physical crosslinking, finally clamping the gel material on two glass plates, sealing silica gel plates on the periphery to prevent water evaporation, and obtaining the thermal response intelligent window with solar spectrum modulation capability. The intelligent window has the advantages of low price of raw materials for preparation, simple preparation means, good stability of window devices and long-term use.
Description
Technical Field
The application belongs to the technical field of gel materials, and particularly relates to preparation of an intelligent window middle interlayer hydrogel with solar spectrum modulation.
Background
The world population growth and rapid modernization have led to increased energy demands, requiring a high degree of energy efficiency. In developing countries, building energy use accounts for 40% of total energy consumption, exceeding that of the industry and transportation sector. Among all building elements, a window is considered one of the least energy efficient parts, because it always performs heat transfer in the opposite direction to the desired direction. Building windows intelligently regulate indoor solar radiation by changing their optical transmittance in response to temperature stimuli are considered to be a promising solution to reduce building energy consumption. The traditional large-area glass (window and glass curtain wall) ensures indoor comfort, good outdoor contact and natural lighting of the building, but cannot adapt to changing weather and seasons, is not energy-saving, causes too much solar energy to flow in, and involves a large amount of heat loss. Static window covering technology, such as blinds and paint, provides some energy savings, as well as visual and thermal comfort to the building user, but does not completely solve this problem. Blinds provide glare control, but are expensive to install. Dynamic glass (smart Electrochromic (EC), thermochromic or photochromic windows) has great promise for applications in building windows, with the possibility of adjusting in real time the solar transmittance (solar intake and solar energy) according to internal and external changes, or simply to the wishes of the occupants. Recently, smart windows have received great attention because of their potentially significant contribution to saving building energy. The window may regulate indoor solar radiation in a "smart" manner, i.e., by dynamically and reversibly regulating the transmission of Ultraviolet (UV), visible, and Infrared (IR) solar radiation. The development of smart windows can be largely divided into electrical, thermal and optical timed optical response changes. Among these, thermal response is distinguished by the fact that no work input devices need to be provided. Recently, energy-saving smart window technology attracts more and more scientific interest, and the exploration of novel energy-saving materials and the combination with practical technology create various required versatility.
Materials for thermochromic smart windows are largely classified into inorganic phase change materials and organic polymer materials. The inorganic phase change material mainly comprises vanadium dioxide, and the phase transition point of the inorganic phase change material can be adjusted by doping other atoms. In general, undoped vanadium dioxide undergoes a phase transition at 68 ℃ and a transition from an insulator to a conductor occurs after the phase transition, so that an increase in the loss of electromagnetic waves in the infrared band in the material results in an increase in the absorption of electromagnetic waves in the infrared band. Essentially, the transformation from the monoclinic phase to the rutile phase occurs, resulting in a significant amount of free electrons within the vanadium dioxide material (NPGAsia Materials,2018,10 (7): 581-605.).
The organic material is mainly a crystalline phase-change polymer film and thermochromic hydrogel, and the hydrogel is a hydrophilic polymer chain network with a water-rich environment and is applied to various fields including bionic engineering, biological implants and drug delivery systems. In recent years, hydrogels are suitable for smart windows using different mechanisms due to their widely tunable chemical and physical properties. The useful properties of the hydrogel material are imparted with the inherent dynamic and reversible nature of its non-covalent interactions, thereby enhancing the performance of the overall smart window system.
Thermochromic hydrogels are particularly excellent materials for smart window applications: most thermochromic hydrogels undergo reversible hydrophilic/hydrophobic phase changes near the Lower Critical Solution Temperature (LCST) (Materials Horizons,2017,4 (2): 109-116.). At temperatures above the LCST, the hydrogen bonds break and then the polymer chains increase and the hydrophobic association becomes effective. However, once the temperature is below the LCST, intermolecular hydrogen bonds become dominant and may dominate between the polymer chains and surrounding water molecules. Thermochromic hydrogels allow the passage of incident light at low temperatures while strongly scattering the incident light at higher temperatures due to the formation of scattering centers of the aggregated polymer particles (Joule, 2019,3 (1): 290-302.).
To achieve optimal energy regulation, two types of radiant heat flux should be considered: solar radiation from the sun and thermal radiation from objects. The polymer has higher solar transmittance at low temperature due to the index matching with water. Beyond the critical temperature, the phase separation of the hydrogel produces strong internal scattering, resulting in low solar transmittance. The spectrum modulation of the solar energy source comprises visible light and near infrared radiation, so that the solar energy source has strong solar energy modulation capability. The water as a high-emissivity material has higher emissivity in a middle infrared band for heat radiation of an object, and the molecular structure of the intelligent window material is reasonably designed, and a group (ACS Applied Materials & Interfaces, 2022) with strong absorption for middle infrared is grafted. The materials can be highly absorbed for the middle infrared rays by matching with each other, so that the high emission for the middle infrared rays is realized, and the materials are particularly aimed at an atmospheric window.
However, it is notable that the previous hydrophobically associating gels were opaque (Chemical Engineeri ng Journal (2019): 325-338;Journal of Polymer Science Part B:Polymer Phys ics 55.13 (2017): 1036-1044;ACS Applied Materials&Interfaces 11.51 (2019): 48428-48436), and high haze made application on smart windows difficult.
The material related by the application is polyvinyl alcohol modified by a short alkane chain, wherein the polyvinyl alcohol (PVA) can be used for various applications due to the mature industrialized production, low cost and biodegradability (please refer to Polymer44 (12) (2003) 3553-3560); butyraldehyde and the like are all extractable from fossil fuels (Polymer Chemistry,2021,12 (34): 4961-4973), but to date there has been no hydrophobic associated physically crosslinked hydrogel with reversible phase change designed by solvent-poor solvent phase inversion and used in smart windows.
Disclosure of Invention
Aiming at the problems in the prior art, the application provides a preparation method of intelligent window interlayer hydrogel with solar spectrum modulation. The method aims to develop a series of hydrophobic association physical crosslinking reversible phase change hydrogels which are low in cost, controllable in phase separation, moldable, high in transparency, mechanically adaptive, recyclable, quick in temperature response, reversible and high in solar spectrum modulation and are based on bulk industrial chemicals, so that the technical problems that the raw materials for preparing intelligent windows in the prior art are high in price, the preparation means are complex, the stability of window devices is poor, the window devices cannot be used for a long time and the like are solved.
In order to achieve the above purpose, the present application provides the following technical solutions:
the technical scheme is as follows: the modified polyvinyl alcohol material is prepared through grafting modification of polyvinyl alcohol with aldehyde compound, termination reaction of the product in saturated sodium bicarbonate solution, eliminating impurity from white solid, and vacuum freeze drying to obtain white grains; wherein the dosage of the aldehyde compound is 30% of the amount of hydroxyl substances in the polyvinyl alcohol.
Further, polyvinyl alcohol was dissolved in dimethyl sulfoxide (DMSO) at 100 ℃, cooled to 60 ℃, and then an acidic catalyst compound was added and stirred for 1 hour.
Still further, the dosage ratio of polyvinyl alcohol to dimethyl sulfoxide (DMSO) was 5 g:200 mL.
Further, the acid catalyst is p-toluenesulfonic acid monohydrate, and the catalyst dosage is 3% of the molar quantity of hydroxyl groups in the polyvinyl alcohol main chain.
The second technical scheme is as follows: the preparation method of the modified polyvinyl alcohol material comprises the following steps:
1) Mixing polyvinyl alcohol with dimethyl sulfoxide (DMSO), heating to dissolve at 100deg.C, cooling the obtained solution to 60deg.C, adding 0.6g of p-toluenesulfonic acid monohydrate, and stirring to obtain activated polyvinyl alcohol solution;
2) 1.85mL of butyraldehyde is added dropwise at the temperature of 60 ℃ to be stirred for reaction for 3 hours, then 500mL of saturated sodium bicarbonate solution (enough sodium bicarbonate solid is added into deionized water until the sodium bicarbonate solid cannot be dissolved any more, and then the solution is filtered to obtain supernatant, namely the saturated sodium bicarbonate solution) is added into the deionized water for termination reaction, white solid is separated out, impurities are removed, and white particles are obtained through vacuum freeze drying, namely the modified polyvinyl alcohol material.
Further, the impurity removal specifically comprises: the white solid was filtered off, washed with deionized water twice daily for 3 days, and then dried in vacuo.
The technical scheme is as follows: the application of the modified polyvinyl alcohol material in the intermediate layer hydrogel with the intelligent window with solar spectrum modulation is provided.
Further, the preparation method of the intelligent window middle interlayer hydrogel with high emissivity and high reversibility and solar spectrum modulation comprises the following steps:
step 1, adding a modified polyvinyl alcohol material into N, N-Dimethylformamide (DMF) at the dosage of 100mg/mL, and stirring for 12h at 90 ℃ until the modified polyvinyl alcohol material is dissolved, thus obtaining a transparent homogeneous solution with the concentration of 100 mg/mL. Then ultrasonic processing is carried out for 30min, degassing is carried out in a vacuum drying box for 1h to completely remove bubbles, centrifugation is carried out, the transparent solution is injected into a custom quartz glass mould with the depth of 4mm by a pouring method, then the custom quartz glass mould is placed in a closed saturated lithium chloride salt solution environment with the humidity of 13% for 7 days at the temperature of 30 ℃, and then the solution is taken out and soaked into water to obtain a transparent gel material, and the process is carried out through continuous exchange and distribution between N, N-dimethylformamide (good solvent) -water vapor (poor solvent) so as to induce polymer chains in the modified polyvinyl alcohol material/N, N-dimethylformamide solution to be entangled and converted into transparent gel;
step 2, stripping the prepared transparent gel from the quartz glass mold, immersing the transparent gel in a large amount of deionized water for at least 3 days, and replacing the deionized water every day to completely remove any soluble substances such as N, N-dimethylformamide and the like, thereby obtaining the intelligent window intermediate layer hydrogel material;
and step 3, placing the high intelligent window intermediate layer hydrogel material in two pieces of glass, sealing edges by using a silica gel plate, and placing water for volatilization, so that the thermal response intelligent window with solar spectrum modulation capability can be obtained.
Compared with the prior art, the application has the following advantages and technical effects:
the application provides a modified polyvinyl alcohol material based on hydrophobic short alkane chain branches, which integrates various properties and is used as an intelligent window intermediate layer hydrogel material. The gel material formed by the method has high transparency, mechanical adaptation, recoverability, quick temperature response, reversibility and high solar spectrum modulation through a non-solvent exchange means under 13% humidity, and the dissociable hydrophobic clusters at high temperature are used as physical crosslinking points, so that the material has the processability adapting to personalized geometric shapes, and more importantly, the material can be recovered and repeatedly prepared, and secondary pollution infection risks and environmental microplastic pollution are avoided.
The polyvinyl alcohol used in the application is low in cost, and aldehyde compounds such as butyraldehyde can be extracted from fossil fuels. The polyvinyl alcohol with certain hydrophobicity and hydrophilicity is modified by butyraldehyde to obtain a high molecular polymer with certain amphipathy, so that the amphipathy is utilized to quench the two-phase component at the initial phase of phase separation in the process of evaporating solvent phase separation in a low humidity environment, and the final gel product is transparent, thereby providing a premise of application in the field of intelligent windows.
Compared with most of previous thermal response hydrogels, the physical crosslinking network of the hydrogel has recoverability and shapeability, and the chain-entangled clusters formed by hydrophobic interaction have excellent mechanical properties, so that the hydrogel has more advantages in future window materials.
The application is an effective and controllable strategy for preparing the hydrophobic association hydrogel by separating the non-solvent phase of the gel material, does not need a cross-linking agent, reduces the defect that chemical substances are not degradable, simultaneously reduces the production cost, does not relate to the technical conditions of 3D printing and the like in the process, has lower requirements on equipment and has simple preparation process.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a flow chart for preparing PVA-C4-window;
FIG. 2 shows the PVA-C4 reaction equation and 1 HNMR spectroscopic analysis;
FIG. 3 is a graph showing the transmittance-temperature relationship of PVA-C4-gel ultraviolet-visible (UV-Vis) spectra;
FIG. 4 is a stress strain curve of PVA-C4-gel;
FIG. 5 is a molding diagram of PVA-C4-gel;
FIG. 6 is a comparison of heat capacities of PVA-C4-gel before and after swelling;
FIG. 7 is MTT toxicity validation of PVA-C4-gel;
FIG. 8 is a graph of performance of PVA-C4-gel before and after recovery;
FIG. 9 is an ultraviolet-visible-infrared spectrum of PVA-C4-window before and after phase transition;
FIG. 10 is an optical modulation factor versus temperature relationship for PVA-C4-window;
FIG. 11 is a graph showing comparison of outdoor test temperatures of PVA-C4-window.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The "normal temperature" and "room temperature" in the present application are all calculated at 25.+ -. 2 ℃ unless otherwise specified.
The application provides a modified polyvinyl alcohol material, which is prepared by grafting and modifying polyvinyl alcohol by using aldehyde compounds, placing the obtained product in saturated sodium bicarbonate solution for termination reaction, removing impurities from precipitated white solid, and performing vacuum freeze drying to obtain white particles, namely the modified polyvinyl alcohol material; wherein the dosage of the aldehyde compound is 30% of the amount of hydroxyl substances in the polyvinyl alcohol.
In some preferred embodiments, the graft modification refers to: polyvinyl alcohol was dissolved in dimethyl sulfoxide (DMSO) at 100 ℃, cooled to 60 ℃, and p-toluenesulfonic acid monohydrate was added and stirred for 1h. The dosage ratio of the polyvinyl alcohol to the dimethyl sulfoxide (DMSO) is 5g to 200mL. The acid catalyst is p-toluenesulfonic acid monohydrate.
The application also provides a preparation method of the modified polyvinyl alcohol material, which comprises the following steps:
1) Mixing polyvinyl alcohol with dimethyl sulfoxide (DMSO), heating to dissolve at 100deg.C, cooling the obtained solution to 60deg.C, adding p-toluenesulfonic acid monohydrate, and stirring to obtain activated polyvinyl alcohol solution; the dosage ratio of polyvinyl alcohol to p-toluenesulfonic acid monohydrate is 5g to 0.6g;
2) 1.85mL of butyraldehyde is added dropwise at 60 ℃ and stirred for reaction for 3 hours, then 500mL of saturated sodium bicarbonate solution (enough sodium bicarbonate solid is added into deionized water until the sodium bicarbonate solid cannot be dissolved any more, and then the solution is filtered to obtain supernatant, namely the saturated sodium bicarbonate solution) is added into the deionized water for termination reaction, white solid is separated out, impurities are removed, and white particles are obtained through vacuum freeze drying, namely the modified polyvinyl alcohol material.
In some preferred embodiments, the removing impurities is specifically: the white solid was filtered off, washed with deionized water twice daily for 3 days, and then dried in vacuo.
The application also provides application of the modified polyvinyl alcohol material in the intelligent window intermediate layer hydrogel with solar spectrum modulation.
In some preferred embodiments, the method for preparing the smart window interlayer hydrogel with high emissivity and high reversibility and solar spectrum modulation comprises the following steps:
step 1, adding a modified polyvinyl alcohol material into N, N-Dimethylformamide (DMF) at the dosage of 100mg/mL, and stirring for 12h at 90 ℃ until the modified polyvinyl alcohol material is dissolved, thus obtaining a transparent homogeneous solution with the concentration of 100 mg/mL. Then carrying out ultrasonic treatment for 30min, degassing in a vacuum drying oven for 1h to completely remove bubbles, centrifuging, injecting the transparent solution into a custom quartz glass mold with the depth of 4mm by a pouring method, and then placing the custom quartz glass mold in a closed saturated lithium chloride salt solution environment for 7 days at the temperature of 30 ℃ to obtain a transparent gel material, wherein the process is carried out by continuously exchanging and distributing N, N-dimethylformamide (good solvent) -water vapor (poor solvent) so as to induce the conversion of the modified polyvinyl alcohol material/N, N-dimethylformamide solution into transparent gel;
step 2, stripping the prepared transparent gel from the quartz glass mold, immersing the transparent gel in a large amount of deionized water for at least 3 days, and replacing the deionized water every day to completely remove any soluble substances such as N, N-dimethylformamide and the like, thereby obtaining the intelligent window intermediate layer hydrogel material;
and step 3, placing the high intelligent window intermediate layer hydrogel material in two pieces of glass, sealing edges by using a silica gel plate, and placing water for volatilization, so that the thermal response intelligent window with solar spectrum modulation capability can be obtained.
The polyvinyl alcohol (PVA) used in the present application is a commercial polyvinyl alcohol having a molecular weight Mw of 146000 to 180000.
The application defines the molded finished gel, the intelligent phase change window middle interlayer, as PVA-Cn-gel.
The low-emissivity glass and the common glass used in the application are purchased in the market.
The temperature recorder used in the application is a Tuo Pu Rui multi-channel data recorder.
The following examples serve as further illustrations of the technical solutions of the application.
Example 1
1. Preparation of modified polyvinyl alcohol material
1) Taking 5g of polyvinyl alcohol (PVA) particles in a 250mL round-bottom flask, adding 200mL of dimethyl sulfoxide (DMSO), and heating at 100 ℃ to dissolve; cooling the PVA solution to 60 ℃, then adding 0.6g of p-toluenesulfonic acid monohydrate, stirring for 1h, and fully dispersing to obtain an activated polyvinyl alcohol solution;
2) Further cooling to 60 ℃, then dropwise adding 1.85mL of butyraldehyde into the polyvinyl alcohol aqueous solution, continuously stirring for 3 hours, and then pouring into 500mL of saturated sodium bicarbonate solution at normal temperature for termination reaction; taking out the precipitated white solid, periodically replacing deionized water for soaking, and cleaning twice a day for three days; finally, white particles are obtained through vacuum freeze drying, and the modified polyvinyl alcohol material is obtained, and the polyvinyl alcohol modified by butyraldehyde is named PVA-C4.
2. Preparation of intelligent phase-change window intermediate interlayer material
1) Adding the prepared PVA-C4 particles into N, N-Dimethylformamide (DMF) to prepare a solution of 100mg/mL, and stirring at 90 ℃ for 12h until the solution is dissolved to obtain a transparent homogeneous solution with the concentration of 100mg/mL; the solution was sonicated (time 30 min) and degassed in a vacuum oven for 1h to completely remove bubbles. Centrifuging on a centrifuge, injecting the transparent solution into a custom quartz glass mold with the depth of 4mm by a pouring method, and exposing the solution in a saturated lithium chloride salt solution environment at 30 ℃ for 7 days to obtain transparent gel;
2) Stripping the transparent gel from the quartz glass mold, immersing in a large amount of deionized water for 3 days, and replacing the deionized water every day to completely remove soluble substances such as N, N-Dimethylformamide (DMF) and the like, thereby obtaining a highly transparent hydrogel film, which is defined as PVA-C4-gel;
3) The highly transparent hydrogel film is placed in two pieces of glass, and is sealed by a silica gel plate to prevent moisture from volatilizing, so that the intelligent phase-change window intermediate layer with solar spectrum modulation capability, which is defined as PVA-C4-window, can be obtained, and the process is shown in a schematic diagram 1.
Performance test:
1. nuclear magnetism
The starting PVA-C4 was characterized on a Bruker400MHz nuclear magnetic resonance apparatus to confirm that post-modification of PVA, i.e., grafting of the short alkane to the polyvinyl alcohol, was completed as follows: use d 6 DMSO is used as a solvent, 6mg PVA-C4 is added to complete dissolution at 70℃, and the dissolution is carried out 1 HNMR spectroscopic analysis, as shown in fig. 2.
As can be seen from FIG. 2, the modification ratio of PVA-C4 was 30% (degree of substitution, DS, DS=2X 2 /(X 1 +2X 2 ) X100%, 2X of the molecule in the formula 2 Represents the number of hydroxyl groups substituted by side chains, denominator X 1 +2X 2 Representing the total hydroxyl number of the polyvinyl alcohol, defining a modification ratio DS as the ratio of the number of substituted hydroxyl groups to the total hydroxyl number), which modification ratio DS is generally determined by 1 The peak integration area of HNMR spectrum is calculated equivalently, i.e., DS will be calculated using the following formula:
A 12 refers to the area of hydrogen atoms contained in carbon number 12, where the value is 1, A 2+4 The areas of hydrogen atoms contained in carbon number 2 and carbon number 4, which are 2.2, are calculated to have a DS of 30%.
The modification rate further ensures that an intelligent phase change window intermediate layer (PVA-C4-gel) has ideal phase change reversibility and long-wave infrared emission, the modification rate is not too high (the solvent is difficult to volatilize and cannot form transparent gel) and also is not too low (the quantity of hydrophobic association side chains is less and cannot be entangled with gel).
2. High light transmittance
The PVA-C4-gel was subjected to ultraviolet-visible (UV) spectroscopy using an ultraviolet-visible spectrophotometer (PerkinElmer Lambda, 950), the spectral range was set to 280-780nm, light transmission (T) was measured, and an optical curve was plotted as shown in FIG. 3. The gel specimens tested were 15mm in diameter and 300 μm thick in thickness.
As can be seen from fig. 3, PVA-C4-gel shows high light transmittance, t=90-92%% at 500 nm.
3. Mechanical properties
The mechanical properties are mainly divided into a tensile test and a unilateral notch test.
And (5) tensile test. The tensile test was carried out on a pearly sea SANS (CMT 2203) machine equipped with a thermostatic water bath at a temperature of 27 ℃. The tensile test uses rectangular gel specimens 20mm long, 8mm wide and 300mm thick. The deformation rate applied in the test was fixed at 0.17s -1 . Three samples were measured for each structure to calculate the mean and standard deviation. From the stress-strain curve, stress (σ), strain (ε), elastic modulus (E), compliance (1/E) were obtained. Sigma is calculated by dividing the force (F) by the cross-sectional area and epsilon is calculated by dividing the stretched length by the original length. The elastic modulus is calculated from the slope of the stress-strain curve with an elongation of greater than 1% to 5%. The tensile work U is calculated from the integral of the stress-strain curve area:
single edge notch test: tensile tests were carried out using two identical samples of length 20mm, width 8mm and thickness 300. Mu.m. Cutting one of the two samples with a razor blade, introducing a gap of length 2mm along the width, where A is the cross-sectional area of the unnotched sample, L 0 Is the initial distance between the jaws. With the same initial dimensions, stress-tensile curves were measured for notched and unnotched samples. Fracture based on single-side crack methodThe energy is as follows:
wherein λc is the elongation at break of the single-sided notched gel.
As can be seen from FIG. 4, PVA-C4-gel shows the characteristics of an elastic material, can realize high strain (the stretching ratio lambda is as high as 22), toughness (the breaking stress sigma f is as high as 1.17 MPa), and high compliance (155 MPa -1 ) High breaking energy (70 KJ m) 2 ) The PVA-C4-gel shows strong mechanical properties, so that the intelligent window prepared from the material has higher mechanical robustness, and a road is paved for the next-generation flexible intelligent window.
4. Thermoplastic Properties
PVA-C4-gel was fixed at both ends of the tensile machine and soaked in 80℃water baths, and stress relaxation was performed while maintaining strains of 50%, 100%, 150%, 200%, 250%, respectively (FIG. 5).
The transparent hydrogel PVA-C4-gel is placed in a matched polytetrafluoroethylene mould (with a base arc radius of 8.6mm and a total diameter of 15 mm) after customized polishing, and is fixed by a stainless steel clip, so that the functions of shaping and balancing pressure are achieved. Then the whole die is placed in hot water at 80 ℃ for 2min, and then the die is quickly transferred into water at 27 ℃ and soaked for 2min. And unloading, namely sequentially removing the clamp, the die and the gel, wherein the obtained transparent film with a certain radian (step is shown in figure 5), and the PVA-C4-gel can realize quick stress relaxation for 1 minute at 80 ℃ in figure 5, so that the PVA-C4-gel can be processed in hot water for a short time to mould a certain shape, has low requirements on equipment, and can meet the requirements on custom windows with different shapes.
5. High heat capacity properties
The good specific heat capacity ensures that the heat storage material can store a large amount of heat, and the relatively high thermal conductivity ensures that the heat stored in the material is uniformly distributed, so that the heat storage efficiency is improved. Some commercial high heat storage materials include paraffin waxes, fatty acids and inorganic salts, which are a class of Phase Change Materials (PCMs), but transparency is important for window applications due to lack of transparency critical to the window.
The application adopts a sapphire method to test the heat capacity of PVA-C4-gel before and after swelling on a low temperature differential scanning calorimeter (DSC 3, metrele-tolidol) platform. As a result, as shown in FIG. 6, it can be seen that the PVA-C4-gel hydrogel after swelling exhibited a higher heat capacity due to the introduction of water (3.1 KJkg -1 K) The intelligent window prepared by the method has strong heat storage performance.
6. Low cytotoxicity
Calpain AM (0.5. Mu.L/mL) and propidium iodide (0.5. Mu.L/mL) were diluted in DPBS to stain, and the medium was removed and added to the wells. The cells were then incubated in a dark environment at 37℃for 30 minutes. Live cells (green staining) and dead cells (red staining) were imaged on days 1, 2 and 3 of culture using an inverted fluorescence microscope (zeiss). WI-38 was cultured at 5000 cells/well in 96-well tissue culture plates (BD Biosciences). The PVA-C4-gel hydrogel was soaked in complete medium at 37℃for 48 hours to prepare a leaching medium. Proliferation of WI-38 was quantified by MTT assay. Absorbance was measured at 450nm with a microplate reader on days 1, 2, and 3 of culture. The results are shown in FIG. 7.
As can be seen from FIG. 7, the bar graph of PVA-C4-gel shows that the material has less cytotoxicity to WI-38 from human embryonic tissue differentiation, has good biocompatibility, and is very suitable as a window material.
7. PVA-C4-gel intelligent response hydrogel recycling process
According to the application, PVA-C4-gel is sheared, dried and dissolved in DMF according to the same concentration to obtain a well-dispersed homogeneous solution. The solution was then poured into a glass mold again and evaporated under 13% humidity to give Re (PVA-C4-gel). From FIG. 8, re (PVA-C4-gel) also maintains this thermal response and excellent mechanical properties.
8. Temperature response in the ultraviolet-visible-infrared spectrum
The ultraviolet-visible-near infrared transmittance spectrum was collected on a UV-Vis-NIR spectrophotometer system with integrating sphere (UV-3600 Plus, shimadzu). The spectrophotometer is connected with the heating table and is used for heating and cooling. The spectrum in the wavelength range (2.5-16 μm) was measured by a fourier transform infrared spectrometer (Nicolet 6700, zemerger fly) and a gold-plated integrating sphere.
As can be seen from FIG. 9, the transmittance spectrum of the window prepared from PVA-C4-window in the 0.28-2.5 μm band has a temperature response, i.e., a high transmittance is maintained before phase transition, and a decrease in transmittance is caused after phase transition due to light scattering points generated by segment collapse in the polymer, as compared with the conventional glass, low emission glass. In the mid-infrared band (8-13 μm), in particular, the atmospheric window band, the emissivity (0.96 (before phase transition)/0.95 (after phase transition)) of the PVA-C4-gel sample in the open window band (8-13 μm) is higher than that of the ordinary glass (0.82) and the low-emission glass (0.57) due to the mid-infrared absorption effect imparted by the-C-O-C-chemical bond in the PVA-C4-gel molecule and the water in the condensed structure. In combination with the foregoing, it is demonstrated that PVA-C4-gel window has advantages over common glass and low emissivity glass in reducing indoor temperature and reducing energy consumption in summer. That is, at lower temperatures, the window is transparent, allowing solar energy to transmit; when heating, the window can automatically block sunlight to cut off solar energy gain. The phase change shows high modulation to sunlight spectrum, and the high emissivity is kept before and after the phase change.
9. PVA-C4-window optical modulation coefficient-temperature relationship
Visible light average transmittance (T) lum ) Near infrared average transmittance T IR Average solar spectrum transmittance (T) sol ) Defined by the following equation:
T lum/IR/sol ＝T lum/IR/sol (@ Low temperature) -T lum/IR/sol (@ high temperature) (6)
Where d is a differential sign and λ is a wavelength.
As can be seen from fig. 10, the transmittance of the smart window to the solar spectrum gradually decreases with the evolution of the phase change process.
10. Outdoor thermal test data comparison of common window materials
The outdoor test compares the energy saving performance of glass panels, low emission glass and PVA-C4-window. It provides an experimental environment for real temperature fluctuations. A box (internal dimensions 15 cm. Times.15 cm. Times.20 cm) with a top glass panel (glass thickness 5mm, dimensions 20 cm. Times.20 cm) was set as a blank, with a thermocouple sensor in the geometric center. The rest of the test apparatus design was identical to the control sample, with the glass panel replaced with low emission glass and PVA-C4-window, respectively. For outdoor demonstration at high temperature, three devices were placed outdoors without any shielding and were directly irradiated with sunlight, and experiments were conducted from 11 pm: 00 starts. Data temperature data was recorded every 10 minutes in Guangzhou.
As can be seen from fig. 11, all windows reached the highest temperature three hours after the start of the experiment, in which the normal glass (blank), the low emission glass and the PVA-C4-window were 87.6 ℃, 78.5 ℃ and 59.6 ℃, respectively, so that the PVA-C4-window maintained the indoor temperature at the lowest level at the highest temperature (14:00), and further saved the energy consumption during the peak period of refrigeration electricity consumption in summer compared with the normal glass window (blank) and the low emission glass window.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (9)
1. A modified polyvinyl alcohol material is characterized in that an aldehyde compound is utilized to carry out grafting modification on polyvinyl alcohol, the obtained product is placed in saturated sodium bicarbonate solution to carry out termination reaction, the precipitated white solid is subjected to impurity removal, and vacuum freeze drying is carried out, so that white particles are obtained, namely the modified polyvinyl alcohol material; wherein the dosage of the aldehyde compound is 30% of the amount of hydroxyl substances in the polyvinyl alcohol.
2. The modified polyvinyl alcohol material according to claim 1, wherein the aldehyde compound is butyraldehyde.
3. The modified polyvinyl alcohol material according to claim 1, wherein the graft modification means: polyvinyl alcohol was dissolved in dimethyl sulfoxide at 100 ℃, cooled to 60 ℃, and then an acidic catalyst was added and stirred for 1h.
4. The modified polyvinyl alcohol material according to claim 3, wherein the dosage ratio of polyvinyl alcohol to dimethyl sulfoxide is 5 g/200 mL.
5. The modified polyvinyl alcohol material according to claim 3, wherein the acidic catalyst is p-toluenesulfonic acid monohydrate and the catalyst is used in an amount of 3% of the molar amount of hydroxyl groups in the polyvinyl alcohol main chain.
6. The method for producing a modified polyvinyl alcohol material according to any one of claims 1 to 5, comprising the steps of:
1) Mixing polyvinyl alcohol with dimethyl sulfoxide, heating and dissolving at 100 ℃, cooling the obtained solution to 60 ℃, adding p-toluenesulfonic acid monohydrate, and stirring to obtain an activated polyvinyl alcohol solution;
2) And (3) dropwise adding a reactant butyraldehyde into the polyvinyl alcohol solution at 60 ℃, stirring and reacting for 3 hours, then pouring into a saturated sodium bicarbonate solution for terminating reaction, separating out white solid, removing impurities, and performing vacuum freeze drying to obtain white particles, namely the modified polyvinyl alcohol material.
7. Use of a modified polyvinyl alcohol material according to any one of claims 1-5 in a smart window interlayer hydrogel with solar spectrum modulation.
8. The use according to claim 7, wherein the method for preparing the smart window intermediate layer hydrogel with high emissivity and high reversibility with solar spectrum modulation comprises the following steps:
dissolving a modified polyvinyl alcohol material in N, N-dimethylformamide at 90 ℃, preserving heat for 12 hours, then carrying out ultrasonic treatment, defoaming, centrifuging, pouring, and then placing in a closed saturated lithium chloride salt solution environment for 7 days to obtain a transparent gel material;
and taking out the transparent gel material, cleaning with deionized water, and then storing in the deionized water to obtain the intelligent window intermediate layer hydrogel material.
9. The use according to claim 8, wherein the modified polyvinyl alcohol material is dissolved in N, N-dimethylformamide at a concentration of 100mg/mL; the environment of the saturated lithium chloride salt solution is maintained to be 13% in humidity, the environment temperature is 30 ℃, and the ultrasonic treatment time is 30min.
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