Preparation method of self-assembled acylated tannic acid, hydrophobic glass and preparation method of hydrophobic glass

Abstract

The invention provides a preparation method of self-assembled acylated tannic acid, hydrophobic glass and a preparation method of the hydrophobic glass, and relates to the technical field of supramolecular assembly.The preparation method of the self-assembled acylated tannic acid comprises the following steps that S11, tannic acid, a catalyst and a first solvent are mixed to obtain a mixture; s12, mixing the mixture with acid anhydride, and carrying out acylation reaction to obtain a product; and S13, washing, purifying and drying the product to obtain the self-assembled acylated tannic acid. According to the technical scheme, the tannic acid, the catalyst and the first solvent are mixed and then mixed with the acid anhydride, the reaction rate is increased, and side reactions are reduced; through precipitation, filtration, dissolution and drying, unreacted raw materials, catalyst residues and side reaction products can be removed, and the purity and stability of the acylated tannic acid are improved, so that the acylated tannic acid has a self-assembly function, and a hydrophobic acylated tannic acid film layer can be formed through self-assembly.

Description

Technical Field

[0001] The present invention relates to the technical field of supramolecular assembly, and in particular to a preparation method of self-assembled acylated tannic acid, hydrophobic glass and a preparation method thereof. Background Art

[0002] Supramolecular assembly is the spontaneous formation of unique nanostructures through dynamic covalent and non-covalent intermolecular interactions (including hydrogen bonding, hydrophobic interactions, electrostatic interactions, van der Waals forces, and π-π stacking). Originating in biological systems, it has a wide range of applications in biomedicine, interfacial modification, and other fields. Tannic acid is a large class of plant-derived biocompatible and biodegradable compounds composed of two or more phenolic units within their structure, which provide abundant reactive sites.

[0003] Currently, supramolecular engineering strategies based on tannic acid are applied to construct various two-dimensional functional metal-phenol network materials, such as capsules or membranes, and are widely used in three-dimensional supramolecular nanomedicines. However, these studies are all based on the assembly of tannic acid, and its modification of the interface is hydrophilic, and its hydrophobic properties are poor. Summary of the Invention

[0004] The main purpose of the present invention is to provide a preparation method of self-assembled acylated tannic acid, hydrophobic glass and its preparation method, aiming to achieve controllable changes in the surface morphology of the glass with the help of multiple solvents, improve the hydrophobicity of the glass, and further realize the self-assembly of acylated tannic acid.

[0005] To achieve the above object, the present invention provides a method for preparing self-assembled acylated tannic acid, comprising the following steps: S11, mixing tannic acid, a catalyst, and a first solvent to obtain a mixture; S12, mixing the mixture with an acid anhydride to undergo an acylation reaction to obtain a product; S13, washing, purifying, and drying the product to obtain self-assembled acylated tannic acid.

[0006] In one embodiment, in step S11, the catalyst includes dimethylaminopyridine; and / or, The first solvent includes at least one of N,N-dimethylformamide and dimethyl sulfoxide.

[0007] In one embodiment, in step S11, the mass concentration of tannic acid in the first solvent is 50-100 g / L; and / or, In step S11, the mass concentration of the catalyst in the first solvent is 0.5-1 g / L.

[0008] In one embodiment, in step S12, the volume ratio of the mixture to the acid anhydride is 30:(1-20); and / or, In step S12, the acylation reaction temperature is 40-80° C., and the reaction time is 1-8 h.

[0009] In one embodiment, step S13 includes: S131, the product is allowed to settle in water, and filtered to obtain a solid; S132. Dissolve the solid in an organic solvent, filter, heat the filtrate, and dry to obtain acylated tannic acid, wherein the organic solvent includes chloroform.

[0010] The present invention also provides a method for preparing hydrophobic glass, comprising the following steps: S20, mixing the self-assembled acylated tannic acid with a second solvent to obtain a hydrophobic solution; S30, providing a glass plate, applying the hydrophobic solution on a surface of the glass plate, and drying the hydrophobic solution to obtain hydrophobic glass; wherein the second solvent comprises at least one of N,N-dimethylformamide, ethanol and chloroform; The self-assembled acylated tannic acid includes the self-assembled acylated tannic acid prepared according to the aforementioned preparation method of the self-assembled acylated tannic acid.

[0011] In one embodiment, in step S20, the concentration of the acylated tannic acid in the second solvent is 0.01-0.1 g / mL.

[0012] In one embodiment, the acid anhydride includes at least one of butyric anhydride, n-hexanoic anhydride, and n-octanoic anhydride.

[0013] In one embodiment, in step S30, the amount of the hydrophobic solution applied to the surface of the glass plate is 2-3 L / m 2 .

[0014] The present invention also provides a hydrophobic glass, which is prepared according to the above-mentioned method for preparing the hydrophobic glass.

[0015] The technical solution of the present invention accelerates the reaction rate and reduces side reactions by mixing tannic acid, a catalyst and a first solvent, and then mixing with an acid anhydride. Unreacted raw materials, catalyst residues and side reaction products can be removed through precipitation, filtration, dissolution and drying, thereby improving the purity and stability of the acylated tannic acid, so that the acylated tannic acid has a self-assembly function, thereby being able to self-assemble to form a hydrophobic acylated tannic acid film layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0017] Figure 1 The tannic acid modified with different carbon chain lengths and the Fourier infrared spectra of tannic acid proposed in the present invention; Figure 2 Optical microscope images of the hydrophobic glass provided in Examples 1, 4, and 7 of the present invention and Comparative Examples 1 and 4; Figure 3 Surface particle size diagram of the hydrophobic glass provided in Examples 1, 4, and 7 of the present invention and Comparative Examples 1 and 4; Figure 4 Optical microscope images of the hydrophobic glass provided in Examples 2, 5, and 8 of the present invention and Comparative Examples 2 and 4; Figure 5 Surface water contact angle diagrams of hydrophobic glass provided in Examples 2, 5, and 8 of the present invention and Comparative Examples 2 and 4; Figure 6 Optical microscope images of the hydrophobic glass provided in Examples 3, 6, and 9 of the present invention and Comparative Examples 3 and 4; Figure 7 Surface spherical size diagrams of the hydrophobic glass provided in Examples 3, 6, and 9 of the present invention and Comparative Examples 3 and 4.

[0018] The purpose, features and advantages of the present invention will be further described with reference to the accompanying drawings and in conjunction with the embodiments. DETAILED DESCRIPTION

[0019] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them.

[0020] It should be noted that, in the embodiments, those without specifying specific conditions, are carried out according to conventional conditions or the conditions recommended by the manufacturer. Those for reagents or instruments used that do not specify the manufacturer are conventional products that can be purchased commercially. In addition, the meaning of "and / or" appearing in the full text includes three parallel schemes. Taking "A and / or B" as an example, it includes schemes A, B, or A and B that meet the same time. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on those of ordinary skill in the art. When the combination of the technical solutions is contradictory or cannot be realized, it should be considered that the combination of such technical solutions does not exist and is not within the scope of protection required by the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work belong to the scope of protection of the present invention.

[0021] Currently, supramolecular engineering strategies based on tannic acid are applied to construct various two-dimensional functional metal-phenol network materials, such as capsules or membranes, and are widely used in three-dimensional supramolecular nanomedicines. However, these studies are all based on the assembly of tannic acid, and its modification of the interface is hydrophilic, and its hydrophobic properties are poor.

[0022] In view of this, the present invention proposes a method for preparing self-assembled acylated tannic acid, comprising the following steps: S11, mixing tannic acid, a catalyst, and a first solvent to obtain a mixture; S12, mixing the mixture with an acid anhydride to undergo an acylation reaction to obtain a product; S13, washing, purifying, and drying the product to obtain self-assembled acylated tannic acid.

[0023] The technical solution of the present invention accelerates the reaction rate and reduces side reactions by mixing tannic acid, a catalyst and a first solvent, and then mixing with an acid anhydride. Unreacted raw materials, catalyst residues and side reaction products can be removed through precipitation, filtration, dissolution and drying, thereby improving the purity and stability of the acylated tannic acid, so that the acylated tannic acid has a self-assembly function, thereby being able to self-assemble to form a hydrophobic acylated tannic acid film layer.

[0024] In one embodiment, in step S11, the catalyst includes dimethylaminopyridine; and / or, The first solvent includes at least one of N,N-dimethylformamide and dimethyl sulfoxide.

[0025] The technical solution of the present invention can significantly improve the rate and selectivity of the acylation reaction by using dimethylaminopyridine as a catalyst. Dimethylaminopyridine has good basicity and steric effect, can effectively promote the acylation reaction between the anhydride and tannic acid, reduce the generation of by-products, and simultaneously improve the yield and purity of the target product. By using N,N-dimethylformamide (DMF) and / or dimethyl sulfoxide (DMSO) as a solvent, it can provide good solubility and reaction medium, so that the reactants can be more evenly dispersed in the solution, thereby promoting the acylation reaction. In addition, these two solvents also have high thermal stability and chemical stability, can remain stable over a wide temperature range, and are conducive to controlling reaction conditions and improving product quality and yield.

[0026] In one embodiment, in step S11, the mass concentration of tannic acid in the first solvent is 50-100 g / L; and / or, In step S11, the mass concentration of the catalyst in the first solvent is 0.5-1 g / L.

[0027] The technical solution of the present invention achieves an optimal solubility of tannic acid by adjusting the mass concentration of tannic acid in the first solvent to 50-100 g / L, thereby ensuring sufficient contact between reactant molecules and improving the efficiency of the acylation reaction. By adjusting the mass concentration of tannic acid, the reaction speed can be effectively controlled to avoid the formation of by-products caused by an overly fast or overly slow reaction. By adjusting the mass concentration of the catalyst in the first solvent to 0.5-1 g / L, the catalyst exhibits optimal catalytic activity within this mass concentration range, can effectively promote the acylation reaction, and improve the yield of the target product.

[0028] In one embodiment, in step S12, the volume ratio of the mixture to the acid anhydride is 30:(1-20); and / or, In step S12, the acylation reaction temperature is 40-80° C., and the reaction time is 1-8 h.

[0029] The technical solution of the present invention achieves an optimal ratio between the acid anhydride and the mixture by adjusting the volume ratio of the mixture to the acid anhydride, thereby ensuring that the acylation reaction is fully carried out, avoiding the occurrence of side reactions caused by excessive acid anhydride, and reducing unnecessary raw material consumption. By adjusting the heating temperature, the acylation reaction can be effectively carried out without generating side reactions or destroying the product structure due to excessively high temperature. By adjusting the heating time, the acylation reaction can be ensured to be completely carried out, avoiding increased energy consumption and extended production cycle caused by prolonged heating.

[0030] In one embodiment, step S13 includes: S131, the product is allowed to settle in water, and filtered to obtain a solid; S132. Dissolve the solid in an organic solvent, filter, heat the filtrate, and dry to obtain acylated tannic acid, wherein the organic solvent includes chloroform.

[0031] The technical solution of the present invention dissolves unreacted reactants in the product by mixing water with the product, thereby precipitating water-insoluble products in the product, facilitating filtration and thereby improving the purity of the resulting acylated tannic acid. Furthermore, by using an organic solvent to dissolve the acylated tannic acid, the acylated tannic acid can be effectively dissolved, while most impurities are not easily soluble in organic solvents. This allows the purification process to effectively remove impurities, further improving the purity of the acylated tannic acid. Specifically, in some embodiments of the present invention, the static precipitation period is 2 hours.

[0032] The present invention also provides a method for preparing hydrophobic glass, comprising the following steps: S20, mixing the self-assembled acylated tannic acid with a second solvent to obtain a hydrophobic solution; S30, providing a glass plate, applying the hydrophobic solution on a surface of the glass plate, and drying the hydrophobic solution to obtain hydrophobic glass; wherein the second solvent comprises at least one of N,N-dimethylformamide, ethanol and chloroform; The self-assembled acylated tannic acid includes the self-assembled acylated tannic acid prepared according to the aforementioned preparation method of the self-assembled acylated tannic acid.

[0033] The technical solution of the present invention comprises modifying tannic acid with anhydride to obtain acylated tannic acid, then dissolving the acylated tannic acid in a second solvent to prepare a hydrophobic solution. When the hydrophobic solution is applied to a glass plate and dried, the second solvent evaporates during the drying process, and the acylated tannic acid self-assembles and adheres to the glass to form a hydrophobic layer, thereby improving the hydrophobicity of the glass. By modifying the tannic acid with anhydride, a hydrophobic carbon chain can be introduced into the tannic acid, thereby further improving the hydrophobicity of the prepared hydrophobic glass.

[0034] In one embodiment, in step S20, the concentration of the acylated tannic acid in the second solvent is 0.01-0.1 g / mL.

[0035] The technical solution of the present invention controls the mass concentration of the acylated tannic acid so that the acylated tannic acid can be fully dissolved in the second solvent, thereby avoiding precipitation or oversaturation caused by excessively high concentration of the acylated tannic acid, thereby improving the uniformity and stability of the hydrophobic solution and further improving the hydrophobic properties of the hydrophobic glass.

[0036] In one embodiment, the acid anhydride includes at least one of butyric anhydride, n-hexanoic anhydride, and n-octanoic anhydride.

[0037] The technical solution of the present invention uses at least one of butyric anhydride, n-hexanoic anhydride and n-octanoic anhydride as an acid anhydride to react with tannic acid, thereby modifying tannic acid by adding carbon chains of different lengths to obtain acylated tannic acid derivatives with different carbon chain lengths. If the carbon chain is too short, the hydrophobic solution cannot form a hydrophobic film; if the carbon chain is too long, the solubility of the acylated tannic acid is low, and a uniform hydrophobic solution cannot be formed.

[0038] In one embodiment, in step S30, the amount of the hydrophobic solution applied to the surface of the glass plate is 2-3 L / m 2 .

[0039] The technical solution of the present invention ensures that the hydrophobic solution is evenly distributed on the surface of the glass plate by controlling the application amount to 2 to 3 liters per square meter, so that the acylated tannic acid in the hydrophobic solution self-assembles on the glass surface and forms a dense hydrophobic layer on the glass surface after drying to obtain hydrophobic glass, thereby improving the hydrophobicity of the hydrophobic glass.

[0040] The present invention also provides a hydrophobic glass, which is prepared according to the above-mentioned method for preparing the hydrophobic glass.

[0041] Since the hydrophobic glass includes all technical solutions of the method for preparing the hydrophobic glass, it also has all the beneficial effects brought by the above solutions, which will not be described in detail here.

[0042] The technical solutions of the present invention are further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0043] Example 1 This embodiment provides a hydrophobic glass, and the steps of the preparation method thereof are as follows: 1. Add 2 g of tannic acid and 0.02 g of dimethylaminopyridine to a beaker containing 30 mL of N,N-dimethylformamide solution. Stir magnetically until dissolved, then transfer to a three-necked flask. Purge nitrogen through the flask continuously for 10 minutes before adding 3 mL of butyric anhydride. The reaction time is 1 hour at 60°C. After the reaction is complete, transfer the product to a large beaker filled with excess deionized water. Stir for 2 hours, filter the precipitated solid, dissolve it in excess chloroform, and remove the chloroform by rotary evaporation (45°C, 80 rpm). Finally, dry the sample in a vacuum at 45°C for 10 hours to obtain butyric anhydride-acylated tannic acid, designated C4 in the figure. 2. Dissolve C4 in N,N-dimethylformamide to a concentration of 0.1 g / mL. Take 5 mL of the C4 N,N-dimethylformamide solution and dry it on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is labeled C4 / DMF in the figure.

[0044] Example 2 This example provides a hydrophobic glass, the preparation method of which is similar to that of Example 1, except that in step 2, C4 is dissolved in ethanol to a solution concentration of 0.1 g / mL, and 5 mL of the C4 ethanol solution is dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is denoted as C4 / ET in the figure.

[0045] Example 3 This embodiment provides a hydrophobic glass, the preparation method of which is similar to that of Example 1, except that in step 2, C4 is dissolved in chloroform to a solution concentration of 0.1 g / mL, and 5 mL of the C4 chloroform solution is dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is denoted as C4 / TCM in the figure.

[0046] Example 4 This embodiment provides a hydrophobic glass, and the steps of the preparation method thereof are as follows: 1. Add 2 g of tannic acid and 0.02 g of dimethylaminopyridine to a beaker containing 30 mL of N,N-dimethylformamide solution. Stir magnetically until dissolved, then transfer to a three-necked flask. Purge nitrogen through the flask continuously for 10 minutes before adding 7 mL of n-hexanoic anhydride. The reaction is continued for 1 hour at 40°C. After the reaction is complete, transfer the product to a large beaker filled with excess deionized water. Stir for 2 hours, filter the precipitated solid, dissolve it in excess chloroform, and remove the chloroform by rotary evaporation (45°C, 80 rpm). Finally, dry the sample in a vacuum at 45°C for 10 hours to obtain butyric anhydride-acylated tannic acid, designated C6 in the figure. 2. Dissolve C6 in N,N-dimethylformamide to a concentration of 0.1 g / mL. Take 5 mL of the C6 N,N-dimethylformamide solution and dry it on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is labeled C6 / DMF in the figure.

[0047] Example 5 This example provides a hydrophobic glass, the preparation method of which is similar to that of Example 4, except that in step 2, C6 is dissolved in ethanol to a solution concentration of 0.1 g / mL, and 5 mL of the C6 ethanol solution is dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is denoted as C6 / ET in the figure.

[0048] Example 6 This example provides a hydrophobic glass, the preparation method of which is similar to that of Example 4, except that in step 2, C6 is dissolved in chloroform to a solution concentration of 0.1 g / mL, and 5 mL of the C6 chloroform solution is dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is denoted as C6 / TCM in the figure.

[0049] Example 7 This embodiment provides a hydrophobic glass, and the steps of the preparation method thereof are as follows: 1. Add 2 g of tannic acid and 0.02 g of dimethylaminopyridine to a beaker containing 30 mL of N,N-dimethylformamide solution. Stir magnetically until dissolved, then transfer to a three-necked flask. Purge nitrogen through the flask continuously for 10 minutes before adding 4 mL of n-octanic anhydride. The reaction is continued for 1 hour at 40°C. After the reaction is complete, transfer the product to a large beaker filled with excess deionized water. Stir for 2 hours, filter the precipitated solid, dissolve it in excess chloroform, and remove the chloroform by rotary evaporation (45°C, 80 rpm). Finally, dry the sample in a vacuum at 45°C for 10 hours to obtain butyric anhydride-acylated tannic acid, designated C8 in the figure. 2. Dissolve C8 in N,N-dimethylformamide to a concentration of 0.1 g / mL. Take 5 mL of the C8 N,N-dimethylformamide solution and dry it on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is labeled C8 / DMF in the figure.

[0050] Example 8 This example provides a hydrophobic glass, the preparation method of which is similar to that of Example 7, except that in step 2, C8 is dissolved in ethanol to a solution concentration of 0.1 g / mL, and 5 mL of the C8 ethanol solution is dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is denoted as C8 / ET in the figure.

[0051] Example 9 This example provides a hydrophobic glass, the preparation method of which is similar to that of Example 7, except that in step 2, C8 is dissolved in chloroform to a solution concentration of 0.1 g / mL, and 5 mL of the C8 chloroform solution is dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is denoted as C8 / TCM in the figure.

[0052] Comparative Example 1 This embodiment provides a hydrophobic glass, and the steps of the preparation method thereof are as follows: Purchase tannic acid, denoted as TA in the figure; Tannic acid was dissolved in N,N-dimethylformamide to a concentration of 0.1 g / mL. 5 mL of the tannic acid N,N-dimethylformamide solution was dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is labeled TA / DMF in the figure.

[0053] Comparative Example 2 This embodiment provides a hydrophobic glass, and the steps of the preparation method thereof are as follows: Tannic acid was dissolved in ethanol to a concentration of 0.1 g / mL. 5 mL of the tannic acid ethanol solution was dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is labeled TA / ET in the figure.

[0054] Comparative Example 3 This embodiment provides a hydrophobic glass, and the steps of the preparation method thereof are as follows: Tannic acid was dissolved in chloroform to a concentration of 0.1 g / mL. 5 mL of the chloroform solution of tannic acid was dried on a 76 mm × 26 mm × 1 mm glass surface to obtain a hydrophobic glass, which is labeled TA / TCM in the figure.

[0055] Comparative Example 4 Ordinary glass purchased without any treatment is marked as Glass in the figure.

[0056] Performance Testing The chemical structure of tannic acid before and after acylation with different chain length anhydrides was analyzed by Fourier transform infrared spectroscopy, and the results were recorded as follows: Figure 1 For TA, the OH stretching vibration of the phenolic hydroxyl group associated with its hydrogen bond causes a peak at 3290 cm -1 There is a broad absorption band at C4, C6, and C8. The hydroxyl stretching vibration peak intensity decreases at ~2953 cm -1 and 2856 cm -1 New methyl and methylene CH stretching vibration peaks appear at 1726 cm -1 The wavelength gradually blue-shifts to ~1770 cm -1 The above changes may be due to the acylation reaction between phenolic hydroxyl group and acid anhydride to form a new ester bond, which also indicates that the alkyl chain of acid anhydride can be combined with tannic acid through covalent bonds.

[0057] The surface morphology of the hydrophobic glass in Examples 1, 4, 7 and Comparative Examples 1 and 4 was observed using an optical microscope, and the images and particle size results were recorded as follows: Figure 2 、 Figure 3 See Figure 2The surface of Comparative Example 4 is smooth and free of impurities. Granularity can be observed on the surface of Comparative Example 1 and Examples 1, 4, and 7. This may be because in the N,N-dimethylformamide solvent, the hydrophilic groups of the acylated tannic acid molecules face outward and the hydrophobic groups face inward. Due to the hydrophobic interaction between the molecules, the molecules aggregate and tend to form particles, realizing the self-assembly of the acylated tannic acid. Figure 3 The particle size of Comparative Example 4 is 0 because there are no particles on the surface. The particle sizes of Comparative Example 1 and Examples 1, 4, and 7 are 4.34±0.80 μm, 5.80±0.78 μm, 3.24±0.37 μm, and 2.67±0.57 μm, respectively.

[0058] The surface morphologies of Examples 2, 5, 8 and Comparative Examples 2 and 4 were observed using an optical microscope, and the results were recorded as follows: Figure 4 As shown, the surface of Comparative Example 4 is smooth and free of impurities, while cracks appear on the surfaces of Comparative Example 2 and Examples 2, 5, and 8. This may be because the acylated tannic acid molecules can be well dissolved in the ethanol solvent, and a film is formed after the ethanol evaporates, thereby achieving self-assembly of the acylated tannic acid.

[0059] The surface hydrophilicity and hydrophobicity of Examples 2, 5, 8 and Comparative Examples 2 and 4 were characterized by using a contact angle meter. The experimental results are as follows: Figure 5 As shown, the surfaces of comparative examples 2 and 4 are hydrophilic, with contact angles (WCA) of 22.57±4.34° and 31.97±3.01°, respectively; the surfaces of examples 2, 5, and 8 are hydrophobic, with contact angles of 78.12±1.68°, 111.66±2.82°, and 94.74±3.72°, respectively, which indicates the successful preparation of hydrophobic glass.

[0060] The surface morphology of Examples 3, 6, 9 and Comparative Examples 3 and 4 was observed using an optical microscope, and the images and particle size results were recorded as follows: Figure 6 、 Figure 7 See Figure 6 The surface of Comparative Example 4 was smooth and free of impurities. Undissolved tannic acid particles were observed in Comparative Example 3. Spherical objects were observed on the surfaces of Examples 3, 6, and 9. This may be because in the chloroform solvent, the hydrophobic groups of the acylated tannic acid molecules face outward and the hydrophilic groups face inward. Due to the intermolecular hydrogen bonding, the molecules assemble and tend to form spheres, realizing the self-assembly of the acylated tannic acid. Figure 7 The particle size of Comparative Example 4 is 0 because there are no particles on the surface. The surface of Comparative Example 3 is undissolved tannic acid particles with a size of 49.60±9.98 μm. The particle sizes of Examples 3, 6, and 9 are 13.95±1.84 μm, 7.08±1.32 μm, and 5.49±0.99 μm, respectively.

[0061] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention specification under the inventive concept of the present invention, or direct / indirect application in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A method for preparing self-assembled acylated tannic acid, characterized in that: The following steps are involved: S11, mixing tannic acid, a catalyst and a first solvent to obtain a mixture; S12, mixing the mixture with an acid anhydride to undergo an acylation reaction to obtain a product; S13, washing, purifying and drying the product to obtain self-assembled acylated tannic acid.

2. The method for preparing the self-assembled acylated tannic acid according to claim 1, characterized in that: In step S11, the catalyst includes dimethylaminopyridine; and / or, The first solvent includes at least one of N,N-dimethylformamide and dimethyl sulfoxide.

3. The method for preparing the self-assembled acylated tannic acid according to claim 2, characterized in that: In step S11, the mass concentration of tannic acid in the first solvent is 50-100 g / L; and / or, In step S11, the mass concentration of the catalyst in the first solvent is 0.5-1 g / L.

4. The method for preparing the self-assembled acylated tannic acid according to claim 2, characterized in that: In step S12, the volume ratio of the mixture to the acid anhydride is 30:(1-20); and / or, In step S12, the acylation reaction is carried out at a temperature of 40 to 80° C. and for a time of 1 to 8 h.

5. The method for preparing the self-assembled acylated tannic acid according to claim 2, characterized in that: Step S13 includes: S131, the product is allowed to settle in water, and a solid is obtained by filtering; S132, dissolving the solid in an organic solvent, filtering, heating the filtrate, and drying to obtain acylated tannic acid, wherein the organic solvent comprises chloroform.

6. A method for preparing hydrophobic glass, characterized in that: The following steps are involved: S20, mixing the self-assembled acylated tannic acid with a second solvent to obtain a hydrophobic solution; S30, providing a glass plate, applying the hydrophobic solution on the surface of the glass plate, and drying the hydrophobic solution to obtain hydrophobic glass; Wherein, the second solvent comprises at least one of N,N-dimethylformamide, ethanol and chloroform; The self-assembled acylated tannic acid comprises the self-assembled acylated tannic acid prepared according to the preparation method of the self-assembled acylated tannic acid according to any one of claims 1 to 5.

7. The method for preparing hydrophobic glass according to claim 2, characterized in that: In step S20, the concentration of the acylated tannic acid in the second solvent is 0.01-0.1 g / mL.

8. The method for preparing hydrophobic glass according to claim 2, wherein: The acid anhydride includes at least one of butyric anhydride, hexanoic anhydride and octanoic anhydride.

9. The method for preparing hydrophobic glass according to claim 2, wherein: In step S30, the amount of the hydrophobic solution applied to the surface of the glass plate is 2-3 L / m 2 .

10. A hydrophobic glass, characterized in that: The hydrophobic glass is prepared according to the method for preparing hydrophobic glass according to any one of claims 6 to 9.

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