阅读说明：本技术 一种三足季铵盐凝胶因子及其超分子智能胶膜的合成和应用 (Tripodal quaternary ammonium salt gelator and synthesis and application of supermolecular intelligent adhesive film thereof ) 是由 林奇 孙小文 王中会 杨海龙 巩冠斐 张芹鹏 姚虹 张有明 魏太保 于 2019-10-31 设计创作，主要内容包括：本发明设计合成了一种三足季铵盐凝胶因子TH,是以对羟基苯甲醛功能化季铵盐和均苯三甲酰肼为原料,在DMF中反应而得,该凝胶因子在加热条件下能在蒸馏水中自组装形成稳定的透明水凝胶TH-G；将该水凝胶均匀铺于玻璃基板上并烘干,即可制得高度透明的智能胶膜TH-GF,其透光率可达97.1%。更神奇的是,该智能胶膜TH-GF用TEA和HCl交替熏蒸可实现透明和不透明之间的可逆切换。因此可以作为智能玻璃覆膜实现对入射光高度透明或完全阻挡,从而动态可逆地调节阳光进入建筑(通过玻璃窗户)的透射率。(The invention designs and synthesizes a tripodia quaternary ammonium salt gel factor TH, which is obtained by taking p-hydroxybenzaldehyde functionalized quaternary ammonium salt and trimesoyl hydrazide as raw materials and reacting in DMF, wherein the gel factor can be self-assembled in distilled water under the heating condition to form stable transparent hydrogel TH-G; the hydrogel is uniformly laid on a glass substrate and dried to obtain the high-transparency intelligent adhesive film TH-GF, and the light transmittance can reach 97.1%. More magical, the intelligent adhesive film TH-GF can realize reversible switching between transparent and opaque by alternately fumigating TEA and HCl. Thus, the coating can be used as a smart glass coating to realize high transparency or complete blocking of incident light, thereby dynamically and reversibly adjusting the transmittance of sunlight entering a building (passing through a glass window).)

1. A tripodia quaternary ammonium salt gelator has the following structural formula:

2. the method for synthesizing tripodal quaternary ammonium salt gelator as claimed in claim 1, wherein trimesoyl hydrazide and p-hydroxybenzaldehyde functionalized quaternary ammonium salt are reacted for 70 ~ 72h at 100 ~ 105 ℃ in a molar ratio of 1:3.3 ~ 1:3.6 in solvent DMF, and a reaction product is recrystallized by DMF and ethyl acetate to obtain a green crystalline solid, namely the tripodal quaternary ammonium salt gelator.

3. The preparation method of the supramolecular intelligent adhesive film based on the tripodal quaternary ammonium salt gelator as claimed in claim 1, is characterized in that: heating and dissolving the tripodia quaternary ammonium salt gel factor in distilled water, and cooling to room temperature to form stable transparent hydrogel; and then uniformly paving the transparent hydrogel on a glass substrate and drying to obtain the highly transparent supermolecule intelligent adhesive film.

4. The method for preparing the supramolecular intelligent adhesive film based on the tripodal quaternary ammonium salt gelator as claimed in claim 3, wherein the gel forming concentration of the tripodal quaternary ammonium salt gelator in distilled water is 0.05 ~ 0.06.06 g/ml.

5. The method for preparing the supramolecular intelligent adhesive film based on the tripodal quaternary ammonium salt gelator as claimed in claim 3, wherein the thickness of the supramolecular hydrogel film is 2.5 ~ 3 x 10^-3mm。

6. The supramolecular smart film prepared by the method of claim 3, wherein: the light transmittance reaches 97.1 percent.

7. The supramolecular smart film as claimed in claim 6, wherein: reversible switching between transparent and opaque can be realized under the alternating action of acid and alkali steam.

8. Use of the supramolecular smart film as claimed in claim 6 for the manufacture of smart glass.

Technical Field

The invention relates to a tripodia quaternary ammonium salt gel factor and a preparation method thereof, and also relates to a property of realizing reversible switching between transparency and opacity based on synthesis of the supermolecular gel factor intelligent adhesive film and under the alternating action of acid-base steam, and the supermolecular gel factor intelligent adhesive film can be used as an intelligent glass coating film to be applied to manufacturing of an intelligent window.

Background

With the continuous development of industrialization, urbanization and modernization, energy consumption worldwide rapidly increases year by year. Therefore, improvement of energy efficiency and reduction of energy consumption play an increasingly important role in the use of building energy. Windows, as an important component of a building, determine lighting, heat insulation, beauty, sound insulation, and natural ventilation. However, conventional windows are limited in their static and non-adaptive nature to dynamic climates, resulting in high building energy consumption. The intelligent glass window has the potential functions of solar energy regulation, coloring, self-cleaning, self-power supply, dehumidification and the like, and is a promising solution for improving the energy-saving efficiency and the indoor comfort level. For example, smart windows may reflect a large portion of incident sunlight during summer, thereby preventing overheating inside buildings. In addition, they can absorb the heat of the sun in winter, helping to keep the room warm. Smart windows, therefore, are a promising way to conserve energy, and can dynamically and reversibly adjust the transmittance of sunlight into a building, providing variable solar heating and visual needs depending on weather changes and personal preferences.

The existing smart window products are often expensive and inferior in quality, and various toxic materials are used in the production process. In recent years, the dynamic property, the reversibility and the self-adaptive property of non-covalent interaction inherent in the intelligent glass constructed by a supramolecular strategy are more and more concerned, so that the constructed intelligent glass has ideal attractive functions.

Disclosure of Invention

The invention aims to provide a tripodia quaternary ammonium salt gelator and a preparation method thereof;

the invention also aims to provide an intelligent adhesive film based on the tripodia quaternary ammonium salt gelator and a preparation method thereof;

the invention also aims to research the reversible optical switching performance of the intelligent adhesive film under the alternating action of acid and alkali steam; the glass is used for manufacturing intelligent glass.

One-and three-footed quaternary ammonium salt gelators and preparation thereof

Synthesis of tripodal quaternary ammonium salt gelator, which is to react trimesoyl hydrazide and functional quaternary ammonium salt of p-hydroxybenzaldehyde in a molar ratio of 1:3.3 ~ 1:3.6 in a solvent DMF (N, N-dimethylformamide) at 100 ~ 105 ℃ for 70 ~ 72h, and to recrystallize a crude product from DMF and ethyl acetate to obtain a green crystalline solid, namely the tripodal quaternary ammonium salt gelator, which is marked as TH.

Wherein, the structural formula of the p-hydroxybenzaldehyde functionalized quaternary ammonium salt is as follows:

the structural formula of trimesoyl hydrazide is as follows:

the structural formula of the tripodia quaternary ammonium salt gelator TH is as follows:

the hydrogen spectrum and the mass spectrum of the tripodal quaternary ammonium salt gel factor (TH) are respectively shown in figures 1 and 2.

Preparation of supermolecule hydrogel and intelligent adhesive film thereof

1. Preparation of supramolecular hydrogels

And heating and dissolving the tripodal quaternary ammonium salt gel factor (TH) in distilled water, and cooling to room temperature to form stable transparent hydrogel which is recorded as TH-G.

The gel forming concentration of the tripodia quaternary ammonium salt gelator in distilled water is 0.05 ~ 0.06.06 g/ml.

The formation mechanism of supramolecular hydrogels: under the heating condition, the tripodal quaternary ammonium salt gel factor (TH) self-assembles in distilled water to form stable transparent hydrogel.

FIG. 3 is a partial concentration nuclear magnetic map of TH. (a) 4.08X 10^-6M；（b）9.16×10^-6M；（c）1.83×10^-5M；（d）2.75×10^-5M；（e）4.58×10^-5And M. In concentration nuclear magnetism, H₅，H₆，H₇Moving to a low field, suggests that TH-G has hydrogen bonding during self-assembly. H₃，H₄Moving to a high field indicates that pi-pi accumulation exists in TH-G during self-assembly. Furthermore, the hydrogen protons on the alkyl chain are all shifted to a high field, suggesting the presence of van der Waals forces during the self-assembly of TH-G.

FIG. 4 shows the IR spectra of TH and TH-G. In the infrared spectrum, the peak of-N-H on TH is from 3442cm^-1Moved to 3437cm^-1-C = O peak from 1674cm^-1Moved to 1670cm^-1Further illustrating the presence of hydrogen bonds in TH-G during self-assembly. Thus, hydrogen bonding, pi-pi stacking and van der Waals forces are present during TH-G self-assembly.

2. Preparation of supermolecule intelligent adhesive film

Uniformly spreading the prepared hydrogel on a glass substrate and drying to obtain a highly transparent supermolecule intelligent adhesive film, wherein the thickness of the adhesive film marked as TH-GF. is generally controlled to be 2.5 ~ 3 × 10^-3mm. The light transmittance can reach 97.1 percent.

Application of supermolecule intelligent hydrogel film in intelligent window

TH-GF was fumigated with TEA (triethylamine, 12 mol/L) steam at 60 ℃ for about 3 minutes and the film was found to change from highly transparent to opaque and the color changed from colorless to opaque white. TH-GF previously fumigated with TEA was then fumigated with HCl (12 mol/L) steam for about 5s and the film was found to change from opaque to clear and also from white to colorless.

FIG. 5 shows SEM pictures of TH-GF (a), TH-GF-TEA (b) and TH-GF-TEA + HCl (c). As shown in FIG. 5a, in the SEM, the microscopic surface structure of TH-GF is uniform and extremely smooth, which indicates that TH-GF can transmit a large amount of incident light, thereby achieving extremely high transparency of the intelligent window. As shown in fig. 5b, the smooth surface of TH-GF (denoted as TH-GF-TEA) becomes a nano-scale microporous structure, so that a large amount of incident light can be reflected or scattered. TH-GF becomes no longer transparent. As shown in FIG. 5, after fumigating TH-GF-TEA with hydrochloric acid vapor, TH-GF becomes transparent again, the TH-GF nano-scale microporous structure disappears, and the TH-GF surface becomes smooth. As shown in fig. 6, the transparency of the smart window was demonstrated to be switchable many times by cycling experiments under the alternating action of TEA and HCl vapors.

FIG. 7 is a graph of IR experiments with TH-GF, TH-GF-TEA and TH-GF-TEA + HCl. In an infrared spectrogram, after TEA steam fumigates TH-GF, the-N-H peak on the TH-GF is from 3437cm^-1Moved to 3443cm^-1-C = O peak from 1670cm^-1Moved to 1665cm^-1It is shown that after TEA acts on TH-GF, hydrogen bonds between TH-GF molecules are destroyed, thereby the smooth surface structure of TH-GF is also destroyed, and the intelligent window becomes opaque. Scanning electron micrographs of TH-GF-TEA also further demonstrate this result. After the TH-GF-TEA is fumigated by HCl steam, the-N-H peak on the TH-GF-TEA is from 3443cm^-1Moved to 3414cm^-1-C = O peak from 1665cm^-1Moved to 1670cm^-1. This result illustrates that hydrogen bonds in the TH-GF are restored again, and the TH-GF restores a smooth surface structure, so that the smart window becomes transparent again.

In conclusion, the invention takes the p-hydroxybenzaldehyde functionalized quaternary ammonium salt and trimesoyl hydrazide as raw materials, and the green crystalline solid tripodal quaternary ammonium salt gel factor TH is obtained by reaction in DMF, and the gel factor can be self-assembled in distilled water under the heating condition to form stable transparent hydrogel TH-G. The hydrogel is uniformly laid on a glass substrate and dried to obtain the high-transparency intelligent adhesive film TH-GF, and the light transmittance can reach 97.1%. More magical, the intelligent adhesive film TH-GF can realize reversible switching between transparent and opaque by alternately fumigating TEA and HCl. Therefore, the glass can be used as a smart glass coating film to realize high transparency or complete blocking of incident light.

Drawings

FIG. 1 shows the hydrogen spectrum of TH.

FIG. 2 is a mass spectrum of TH.

FIG. 3 is a partial concentration nuclear magnetic map of TH.

FIG. 4 is an infrared experimental chart of TH and TH-G.

FIG. 5 is a scanning electron micrograph of TH-GF, TH-GF-TEA and TH-GF-TEA + HCl.

FIG. 6 is a cycle chart of reversible optical light opening of the supramolecular intelligent hydrogel film.

FIG. 7 is a graph of IR experiments with TH-GF, TH-GF-TEA and TH-GF-TEA + HCl.

Detailed Description

The synthesis and application of the tripodal quaternary ammonium salt gelator, the supramolecular intelligent hydrogel and the transparent intelligent window film are further described by specific examples.