Amphiphilic covalent organic framework material as well as preparation method and application thereof

Abstract

The invention discloses an amphiphilic covalent organic framework material as well as a preparation method and application thereof, relates to a covalent organic framework material as well as a preparation method and application thereof, and aims to solve the technical problems of single structure type, poor amphiphilic property, low emulsifying property and poor emulsion stability of the conventional amphiphilic COFs. The basic structural unit of the amphiphilic covalent organic framework material is # imgabs0 #, wherein n is equal to 8 or 12, and m is equal to 0 or 1; the compound is synthesized from sulfonic acid diamine, phenanthroimidazole diamine and 4, 4 ', 4' '-[(1, 3, 5-triazine-2, 4, 6-triyl) tri (oxy)] tribenzaldehyde, the water contact angle of the compound is 28.26-45.66 degrees, the oil contact angle of the compound is 10.66-22.06 degrees, and the compound can be used in the field of emulsifiers.

Description

Technical Field

[0001] The present invention relates to covalent organic framework materials and their preparation methods and applications, belonging to the technical field of emulsifiers. Background Art

[0002] An emulsion is a dispersion system composed of two immiscible liquids and is often used in industrial production and scientific research. Traditional emulsifiers mainly consist of ionic or non-ionic surfactants, which can promote the formation of a relatively uniform and stable interface between the two phases. However, the interfacial energy of surfactants is relatively high, and the formed emulsion system is relatively unstable. Therefore, it is of great significance to explore new materials for constructing stable emulsion systems. In contrast, covalent organic frameworks (COFs) materials have advantages such as high specific surface area, high porosity, easy modification of topological structures, and structural stability, making amphiphilic COFs materials have great application potential in the field of emulsifiers. In recent years, the application of amphiphilic materials in emulsion systems has been successively reported. Ye Zhuangjie et al. reported an amphiphilic nanoparticle containing sulfonate groups for stabilizing foams in "Contemporary Chemical Industry", Vol. 52, No. 9, pp. 2111-2118, September 2023. However, the contact angles of this material are 108.5°, 104.5°, 97.5°, and 88°, and the amphiphilic properties of the material are poor; Chinese Patent with Publication No. CN 116731341A discloses a COFs material that can stabilize high internal phase Pickering emulsions. However, a large amount of rare and precious metal salts such as scandium and bismuth need to be introduced during the preparation process, which is expensive, and the structure is traditional and single, with only aldehyde groups as a functional group, which is not conducive to the step-by-step adjustment of material properties; Chinese Patent with Publication No. CN 114634801A discloses an amphiphilic nano-silica solid emulsifier for oil-based drilling fluids. The test results show that 1 / 4 of the oil-water mixture still cannot be stably emulsified, and the stability is poor.

[0003] In the related work reported currently, the amphiphilic materials used to stabilize emulsions mainly have the following defects:

[0004] 1. The emulsifying property and emulsion stability of amphiphilic materials are poor;

[0005] 2. The types of amphiphilic COFs structures are single;

[0006] 3. The amphiphilic properties of COFs are poor. Summary of the Invention

[0007] The present invention aims to solve the technical problems of the current single type of amphiphilic COF structures, poor amphiphilic properties, low emulsifying performance, and poor emulsion stability, and provides an amphiphilic covalent organic framework material, a preparation method thereof, and an application thereof. The amphiphilic covalent organic framework material of the present invention is an amphiphilic covalent organic framework material with an alkyl chain as the hydrophobic group and a sulfonic acid group as the hydrophilic group, and the two groups act synergistically.

[0008] The basic structural unit of the amphiphilic covalent organic framework material of the present invention is:

[0009]

[0010] , where n = 8 or 12, and m = 0 or 1.

[0011] The preparation method of the above-mentioned amphiphilic covalent organic framework material is carried out according to the following steps:

[0012] First, diamine sulfonate, phenanthroimidazole diamine, and 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde (TFPT) are weighed respectively according to the molar ratio of (1 - 3):(1 - 3):4, added to a Pyrex tube, and then an organic solvent I and a catalyst are added, and mixed evenly;

[0013] Second, the Pyrex tube is subjected to a cycle of vacuum pumping - nitrogen filling operations to keep a nitrogen environment inside the Pyrex tube;

[0014] Third, the Pyrex tube is heated to 100 - 200 °C and maintained for 1 - 7 days for reaction;

[0015] Fourth, after the reaction is completed, it is cooled to room temperature, the reaction system is filtered by suction, the filter cake is taken, washed repeatedly with an organic solvent II, the filter cake is collected and dried in vacuum, and an amphiphilic covalent organic framework material is obtained.

[0016] Furthermore, the organic solvent I in step one is o-dichlorobenzene, n-butanol, mesitylene, dioxane, N,N-dimethylformamide, acetic acid, polyethylene, or dimethyl sulfoxide.

[0017] Furthermore, the catalyst in step one is glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, concentrated hydrochloric acid with a mass percentage concentration of 30% - 37%, or concentrated sulfuric acid with a mass percentage concentration of 95% - 98%.

[0018] Furthermore, the diamine sulfonate in step one is 2,5-diaminobenzene-1,4-disulfonic acid or 2,5-diaminobenzenesulfonic acid. The CAS number of 2,5-diaminobenzene-1,4-disulfonic acid: 7139-89-1; the CAS number of 2,5-diaminobenzenesulfonic acid: 88-45-9.

[0019] Further, the phenanthroimidazole diamine described in Step 1 is 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C8) or 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C 12 )

[0020] The synthesis method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C8) is as follows:

[0021] (1) First, concentrated HNO3 with a mass percentage concentration of 63% - 65%, concentrated H2SO4 with a mass percentage concentration of 95% - 98% and 9,10-phenanthrenequinone are reacted at 80 - 150 °C for 12 - 96 hours to obtain a pale yellow solid 2,7-dinitro-9,10-phenanthrenequinone;

[0022] (2) Then, 2,7-dinitro-9,10-phenanthrenequinone, ammonium acetate and 4-n-octyloxybenzaldehyde are reacted to obtain 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro (NO2-PIP-C8);

[0023] (3) Then, 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro and 2,7-dinitro-9,10-phenanthrenequinone are added to hydrazine hydrate and reacted at 60 - 120 °C for 12 - 36 hours to obtain 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C8). The reaction formula is as follows:

[0024]

[0025]

[0026] The synthesis method of 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C 12 ) is as follows:

[0027] (1) First, concentrated HNO3 with a mass percentage concentration of 63% - 65%, concentrated H2SO4 with a mass percentage concentration of 95% - 98% and 9,10-phenanthrenequinone are reacted at 80 - 150 °C for 12 - 96 hours to obtain a pale yellow solid 2,7-dinitro-9,10-phenanthrenequinone;

[0028] (2) React 2,7-dinitro-9,10-phenanthrenequinone, ammonium acetate with 4-dodecyloxybenzaldehyde to obtain 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro (NO2-PIP-C 12 );

[0029] (3) Then add 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro and 2,7-dinitro-9,10-phenanthrenequinone to hydrazine hydrate, and react at 60 - 120 °C for 12 - 36 hours to obtain 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C 12 ). The reaction formula is as follows:

[0030]

[0031] Furthermore, the molar ratio of the phenanthroimidazole diamine described in step one to the volume of organic solvent I is 0.15 mmol:(0.5 - 1.0) mL.

[0032] Furthermore, the molar ratio of the phenanthroimidazole diamine described in step one to the volume of the catalyst is 0.15 mmol:(0.2 - 0.5) mL.

[0033] The organic solvent II described in step four is one or a combination of two of acetone, ethanol, methanol, tetrahydrofuran, ethyl acetate, dichloromethane or 1,2-dichloroethane.

[0034] The application of the above amphiphilic covalent organic framework material is to use the amphiphilic covalent organic framework material as an emulsifier for oil-water two-phase emulsification.

[0035] This application provides an amphiphilic covalent organic framework for oil-water emulsification and stabilization and its preparation method. This amphiphilic covalent organic framework is a COFs material with a novel three-component structure containing the synergistic effect of long-chain alkyl and sulfonic acid groups. The raw materials for preparation are cheap and easy to obtain, the post-treatment is simple, without complex operations or expensive process equipment, the production cost is low, and it is easy to prepare in batches. The prepared hydrophobic COFs material has advantages such as stability and controllable pore size, and can regulate the oil-water emulsification performance at the molecular level. The average water contact angle of the amphiphilic covalent organic framework material of the present invention is 28.26° - 45.66°, and the average oil contact angle is 10.66° - 22.06°. The amphiphilic covalent organic framework material of the present invention can be used in the field of emulsifiers. Description of the Drawings

[0036] Figure 1FT-IR spectra of 2,5-diamino-1,4-benzenedisulfonic acid, 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde and the amphiphilic covalent organic framework material in Example 1, where the abscissa is the wave number and the ordinate is the transmittance;

[0037] Figure 2 Photographs of the water contact angle and oil contact angle of the amphiphilic covalent organic framework material prepared in Example 1;

[0038] Figure 3 Naked-eye observation effect diagrams of the emulsification effects of the amphiphilic covalent organic framework material prepared in Example 1 on the oil-water mixture of soybean oil and the oil-water mixture of castor oil.

[0039] Figure 4 Optical microscope observation effect diagrams of the emulsification effects before and after the amphiphilic covalent organic framework material prepared in Example 1 on the oil-water mixture of castor oil.

[0040] Figure 5 Emulsification effect diagrams of different masses of an amphiphilic covalent organic framework material prepared in Example 1 for the mixing of oil phase and water phase. Detailed implementation manners

[0041] The following examples are used to verify the beneficial effects of the present invention:

[0042] Example 1: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0043] I. Weigh 0.045 mol of 2,5-diaminobenzene-1,4-disulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde (TFPT), and add them to a Pyrex tube. Then add 1.0 mL of n-butanol and 1.0 mL of mesitylene as solvents, and then add 0.2 mol of glacial acetic acid as a catalyst, and mix evenly;

[0044] The preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is as follows:

[0045] (1) First, react 60 mL of concentrated HNO3 with a mass percentage concentration of 63%, 6 mL of concentrated H2SO4 with a mass percentage concentration of 98% and 3 mol of 9,10-phenanthrenequinone at 120 °C for 72 hours to obtain a pale yellow solid 2,7-dinitro-9,10-phenanthrenequinone;

[0046] (2) React 1 mol of 2,7-dinitro-9,10-phenanthrenequinone, 4 mol of ammonium acetate and 1 mol of 4-n-octyloxybenzaldehyde at 160 °C for 96 hours, and the obtained dinitrophenanthroimidazole is 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro (NO2-PIP-C8);

[0047] (3) React 1 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro (NO2-PIP-C8) with 15 mL of hydrazine hydrate at 80 °C for 24 hours, and the obtained phenanthroimidazole diamine is 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C8);

[0048] II. Perform a vacuum-nitrogen filling cycle operation on the Pyrex tube to keep a nitrogen environment inside the Pyrex tube;

[0049] III. Heat the Pyrex tube to 120 °C and keep it for 3 days for reaction;

[0050] IV. After the reaction is completed, cool it to room temperature, filter the reaction system by suction, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain an amphiphilic covalent organic framework material.

[0051] In this example, the yield of the amphiphilic covalent organic framework material is 75%.

[0052] The synthesis reaction formula of the amphiphilic covalent organic framework material in this example is as follows:

[0053]

[0054]

[0055] Perform structural characterization on the amphiphilic covalent organic framework material prepared in Example 1 by Fourier transform infrared spectroscopy, and the obtained infrared spectrum is as Figure 1 shown. From Figure 1 it can be seen that at 1190 cm -1 there is a stretching vibration absorption peak of S–O, at 1608 cm -1 there is a stretching vibration absorption peak of C=N, and partial stretching vibration of -(CH3)4- near 720 cm -1 indicates the introduction of long-chain alkyl groups in the organic ligand into the material, indicating the successful preparation of this amphiphilic covalent organic framework material.

[0056] The amphiphilic covalent organic framework material prepared in Example 1 was subjected to contact angle detection using a contact angle measuring instrument. The specific method was carried out according to the following steps:

[0057] I. Take 50 mg of the amphiphilic covalent organic framework material and evenly spread it in the groove of the tablet press. Press it with a hydraulic tablet press to obtain a material tablet.

[0058] II. Place the material tablet made in step I on the contact angle platform. Drop a drop of distilled water on the surface of the material tablet with a capillary tube, and quickly take a picture and record the contact angle with a contact angle measuring instrument. The average value of 6 test results is 42.16°. The contact angle photo is as shown in Figure 2 a of

[0059] III. Record the degrees of the contact angles when the liquid droplet stays for 0 s, 10 min, 30 min, and 1 h, which are 46.18°, 11.68°, 0°, and 0° respectively, proving that the amphiphilic covalent organic framework material prepared in Example 1 is hydrophilic.

[0060] IV. Place the material tablet made in step I on the contact angle platform. Drop a drop of castor oil on the surface of the material tablet with a capillary tube, and quickly take a picture and record the contact angle with a contact angle measuring instrument. The average value of 6 test results is 11.04°. The contact angle photo is as shown in Figure 2 b of

[0061] V. Record the contact angle degrees when the liquid droplet stays for 0 s, 10 min, 30 min, and 1 h, which are 12.64°, 10.98°, 10.04°, and 10.02° respectively, proving that the amphiphilic covalent organic framework material prepared in Example 1 is also lipophilic and it is an amphiphilic material.

[0062] The amphiphilic covalent organic framework material prepared in Example 1 was subjected to emulsification test by naked eye observation as follows:

[0063] Take 5 ml of distilled water and 5 ml of soybean oil and mix them. Shake and ultrasonicate to make them uniformly dispersed and mixed as the blank control group to obtain the mixed phase I. Then take 5 ml of distilled water and 5 ml of soybean oil and mix them, and then add 20 mg of the ground and evenly dispersed amphiphilic covalent organic framework material. Disperse and mix under the same shaking and ultrasonication conditions to obtain emulsion I. Figure 3 The first control group is the naked eye observation effect diagram of the emulsification effect of the amphiphilic covalent organic framework material prepared in Example 1 on the oil-water mixture of soybean oil. According to Figure 3 the first group of control groups, it can be seen that the oil and water phases in the mixed phase I quickly separate, while the emulsion I is fine and milky without large droplets. It is determined that this amphiphilic covalent organic framework material has good emulsification.

[0064] Take 5 ml of distilled water and 5 ml of castor oil respectively, mix them, shake and sonicate them to make them evenly dispersed and mixed, as a blank control group, to obtain mixed phase II; then take 5 ml of distilled water and 5 ml of castor oil respectively, mix them, add 20 mg of evenly ground amphiphilic covalent organic framework material, shake and sonicate them under the same conditions to make them evenly dispersed and mixed, to obtain emulsion II. Figure 3 The second control group is a naked eye observation effect diagram of the emulsification effect of the amphiphilic covalent organic framework material prepared in Example 1 on the oil-water mixture of castor oil. Figure 3 From the second control group, it can be seen that the oil and water phases in the mixed phase II separated rapidly, while the emulsion II was smooth and creamy without large droplets, which indicates that the amphiphilic covalent organic framework material has good emulsification properties.

[0065] Using a microscope Figure 3 The mixed phase II and emulsion II in the second control group were compared and observed. Figure 4 As shown, from Figure 4 It can be observed that the number of droplets in emulsion II is significantly greater than that in mixed phase II, and the distribution is more uniform, indicating that the amphiphilic covalent organic framework material has good emulsification properties.

[0066] The stability of the amphiphilic covalent organic framework material prepared in Example 1 was tested by naked eye observation control, as follows:

[0067] 1. Take 5 ml of distilled water and 5 ml of castor oil respectively, mix them, shake and ultrasonicate them to make them evenly dispersed and mixed, as a blank control group, to obtain mixed phase I;

[0068] 2. Take 5 ml of distilled water and 5 ml of castor oil respectively, mix them, add 5 mg of evenly ground amphiphilic covalent organic framework material, shake and ultrasonicate to make it evenly dispersed and mixed, and obtain emulsion III;

[0069] 3. Take 5 ml of distilled water and 5 ml of castor oil respectively, mix them, add 10 mg of evenly ground amphiphilic covalent organic framework material, shake and ultrasonicate to make it evenly dispersed and mixed, and obtain emulsion IV;

[0070] 4. Take 5 ml of distilled water and 5 ml of castor oil respectively, mix them, add 20 mg of the evenly ground amphiphilic covalent organic framework material, shake and ultrasonicate to make it evenly dispersed and mixed, and obtain emulsion V;

[0071] 5. Take 5 ml of distilled water and 5 ml of castor oil respectively, mix them, add 30 mg of the evenly ground amphiphilic covalent organic framework material, shake and ultrasonicate to make it evenly dispersed and mixed, and obtain emulsion VI;

[0072] The mixed phase I, emulsion III, emulsion IV, emulsion V, and emulsion VI were left standing at room temperature of 25°C, and the stability of emulsion III was observed and recorded at 30 min, 2 h, 1 d, and 2 d of stability respectively. The stability effect diagram is as Figure 5 shown. It was Figure 5 observed that larger droplets rapidly appeared in the mixed phase I and the oil and water phases were stratified. Slight oil-water interface stratification occurred in emulsion III after standing for 2 h, oil-water interface stratification occurred in emulsion IV after standing for 1 d, oil-water interface stratification occurred in emulsion V after standing for 2 d, while emulsion VI still remained a stable and uniform emulsion after standing for 2 d. It was then determined that this amphiphilic covalent organic framework material had good emulsion stability, and the greater the amount of the material, the stronger the emulsion stability.

[0073] Example 2: The preparation method of the amphiphilic covalent organic framework material in this example was carried out according to the following steps:

[0074] I. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to a Pyrex tube. Then add 1.2 mL of n-butanol and 0.8 mL of dioxane as solvents, and add 0.3 mL of glacial acetic acid as a catalyst, and mix evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine was the same as that in Example 1;

[0075] II. Perform a vacuum-nitrogen filling cycle operation on the Pyrex tube to keep a nitrogen environment inside the Pyrex tube;

[0076] III. Heat the Pyrex tube to 130°C and keep it for 5 days for reaction;

[0077] IV. After the reaction is completed, cool it to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80°C for vacuum drying for 72 hours to obtain the amphiphilic covalent organic framework material.

[0078] The yield of the amphiphilic covalent organic framework material in this example was 84%.

[0079] The amphiphilic covalent organic framework material prepared in Example 2 was made into a tablet, and the contact angle was measured. The average value of the 6 water contact angles was 45.66°, and the average value of the oil contact angle was 11.28°. It is an amphiphilic material.

[0080] Example 3: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0081] I. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them into a Pyrex tube. Then add 1.6 mL of N,N-dimethylformamide and 0.4 mL of o-dichlorobenzene as solvents, and add 0.4 mL of glacial acetic acid as a catalyst, and mix evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0082] II. Perform a vacuum-nitrogen filling cycle operation on the Pyrex tube to keep a nitrogen environment inside the Pyrex tube;

[0083] III. Heat the Pyrex tube to 150 °C and keep it for 5 days for reaction;

[0084] IV. After the reaction is completed, cool it to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain the amphiphilic covalent organic framework material.

[0085] The yield of the amphiphilic covalent organic framework material in this example is 78%.

[0086] Press the amphiphilic covalent organic framework material prepared in Example 3 into a tablet and measure the contact angle. The average value of the 6 water contact angles is 44.46°, and the average value of the oil contact angle is 12.88°.

[0087] Example 4: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0088] 1. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to a Pyrex tube. Then add 1.4 mL of dimethyl sulfoxide and 0.6 mL of N,N-dimethylformamide as solvents, and further add 0.2 mL of glacial acetic acid as a catalyst, and mix them evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0089] 2. Perform a vacuum-nitrogen filling cycle on the Pyrex tube to maintain a nitrogen environment inside the Pyrex tube;

[0090] 3. Heat the Pyrex tube to 160 °C and keep it for 3 days for reaction;

[0091] 4. After the reaction is completed, cool it to room temperature, filter the reaction system by suction, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain an amphiphilic covalent organic framework material.

[0092] In this example, the yield of the amphiphilic covalent organic framework material is 80%.

[0093] Press the amphiphilic covalent organic framework material prepared in Example 4 into a tablet and measure the contact angle. The average value of the 6 water contact angles is 40.36°, and the average value of the oil contact angle is 10.06°.

[0094] Example 5: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0095] 1. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to a Pyrex tube. Then add 1.5 mL of dioxane and 0.5 mL of mesitylene as solvents, and further add 0.3 mL of glacial acetic acid as a catalyst, and mix them evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0096] II. Conduct a vacuum-nitrogen filling cycle operation on the Pyrex tube to maintain a nitrogen environment inside the Pyrex tube;

[0097] III. Heat the Pyrex tube to 130 °C and maintain for 3 days for reaction;

[0098] IV. After the reaction is completed, cool to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain the amphiphilic covalent organic framework material.

[0099] In this example, the yield of the amphiphilic covalent organic framework material is 83%.

[0100] Make the amphiphilic covalent organic framework material prepared in Example 5 into a tablet and measure the contact angle. The average value of the 6 water contact angles is 51.89°, and the average value of the oil contact angles is 21.23°.

[0101] Example 6: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0102] I. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to the Pyrex tube. Then add 1.8 mL of mesitylene and 0.2 mL of dimethyl sulfoxide as solvents, and then add 0.4 mL of glacial acetic acid as a catalyst, and mix evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0103] II. Conduct a vacuum-nitrogen filling cycle operation on the Pyrex tube to maintain a nitrogen environment inside the Pyrex tube;

[0104] III. Heat the Pyrex tube to 160 °C and maintain for 3 days for reaction;

[0105] IV. After the reaction is completed, cool to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain the amphiphilic covalent organic framework material.

[0106] In this example, the yield of the amphiphilic covalent organic framework material is 77%.

[0107] The amphiphilic covalent organic framework material prepared in Example 6 was made into a tablet, and the contact angle was measured. The average value of the water contact angle for 6 times was 36.98°, and the average value of the oil contact angle was 22.06°.

[0108] Example 7: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0109] I. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to a Pyrex tube. Then add 0.8 mL of mesitylene and 1.2 mL of ortho-dichlorobenzene as solvents, and then add 0.16 mL of glacial acetic acid as a catalyst, and mix evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0110] II. Perform a vacuum-nitrogen filling cycle operation on the Pyrex tube to keep a nitrogen environment inside the Pyrex tube;

[0111] III. Heat the Pyrex tube to 140 °C and keep it for 3 days for reaction;

[0112] IV. After the reaction is completed, cool it to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain the amphiphilic covalent organic framework material.

[0113] The yield of the amphiphilic covalent organic framework material in this example is 88%.

[0114] The amphiphilic covalent organic framework material prepared in Example 7 was made into a tablet, and the contact angle was measured. The average value of the water contact angle for 6 times was 39.23°, and the average value of the oil contact angle was 10.68°.

[0115] Example 8: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0116] 1. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to a Pyrex tube. Then add 0.6 mL of n-butanol and 1.4 mL of N,N-dimethylformamide as solvents, and further add 0.2 mL of glacial acetic acid as a catalyst, and mix them evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0117] 2. Perform a vacuum-nitrogen filling cycle on the Pyrex tube to maintain a nitrogen environment inside the Pyrex tube;

[0118] 3. Heat the Pyrex tube to 110 °C and maintain for 3 days for reaction;

[0119] 4. After the reaction is completed, cool to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain an amphiphilic covalent organic framework material.

[0120] In this example, the yield of the amphiphilic covalent organic framework material is 90%.

[0121] Press the amphiphilic covalent organic framework material prepared in Example 8 into a tablet and measure the contact angle. The average value of the 6 water contact angles is 29.76°, and the average value of the oil contact angles is 13.29°.

[0122] Example 9: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0123] 1. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to a Pyrex tube. Then add 0.4 mL of N,N-dimethylformamide and 1.6 mL of dioxane as solvents, and further add 0.3 mol of glacial acetic acid as a catalyst, and mix them evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0124] II. Perform a vacuum-nitrogen filling cycle on the Pyrex tube to maintain a nitrogen environment inside the Pyrex tube;

[0125] III. Heat the Pyrex tube to 145 °C and hold for 3 days for reaction;

[0126] IV. After the reaction is completed, cool to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain an amphiphilic covalent organic framework material.

[0127] In this example, the yield of the amphiphilic covalent organic framework material is 81%.

[0128] Make the amphiphilic covalent organic framework material prepared in Example 9 into a tablet and measure the contact angle. The average value of the 6 water contact angles is 30.23°, and the average value of the oil contact angle is 15.33°.

[0129] Example 10: The preparation method of the amphiphilic covalent organic framework material in this example is carried out according to the following steps:

[0130] I. Weigh 0.045 mol of 2,5-diamino-1,4-benzenedisulfonic acid, 0.045 mol of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine, and 0.06 mol of 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde, and add them to the Pyrex tube. Then add 0.2 mL of n-butanol and 1.8 mL of dioxane as solvents, and then add 0.4 mL of glacial acetic acid as a catalyst, and mix evenly; the preparation method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is the same as that in Example 1;

[0131] II. Perform a vacuum-nitrogen filling cycle on the Pyrex tube to maintain a nitrogen environment inside the Pyrex tube;

[0132] III. Heat the Pyrex tube to 110 °C and hold for 3 days for reaction;

[0133] IV. After the reaction is completed, cool to room temperature, perform suction filtration on the reaction system, take the filter cake, wash it 3 times with a mixed solvent of acetone and ethanol with a volume ratio of 1:1, and then place it in a vacuum oven at 80 °C for vacuum drying for 72 hours to obtain an amphiphilic covalent organic framework material.

[0134] In this example, the yield of the amphiphilic covalent organic framework material is 88%.

[0135] The amphiphilic covalent organic framework material prepared in Example 10 was made into a tablet, and the contact angle was measured. The average value of the water contact angle for 6 times was 28.26°, and the average value of the oil contact angle was 10.66°.

Claims

1. An amphiphilic covalent organic framework material, characterized in that The basic structural unit of the material is: where n = 8 or 12, and m = 0 or 1.

2. A method for preparing an amphiphilic covalent organic framework material according to claim 1, characterized in that, The method is carried out according to the following steps:

1. Weigh sulfonic diamine, phenanthroimidazole diamine and 4,4′,4″-[(1,3,5-triazine-2,4,6-triyl)tris(oxy)]tribenzaldehyde according to the molar ratio of (1 - 3):(1 - 3):4 respectively, add them into a Pyrex tube, then add organic solvent I and a catalyst, and mix them evenly; 2. Carry out a cycle operation of evacuating and filling nitrogen in the Pyrex tube to keep a nitrogen environment inside the Pyrex tube; 3. Heat the Pyrex tube to 100 - 200 °C and keep it for 1 - 7 days for reaction; 4. After the reaction is completed, cool it to room temperature, filter the reaction system by suction, take the filter cake, wash it repeatedly with organic solvent II, collect the filter cake and dry it under vacuum to obtain the amphiphilic covalent organic framework material.

3. The preparation method of an amphiphilic covalent organic framework material according to claim 2, wherein, The organic solvent I described in step 1 is one or a combination of two of o-dichlorobenzene, n-butanol, mesitylene, dioxane, N,N-dimethylformamide, acetic acid, polyethylene and dimethyl sulfoxide.

4. The preparation method of an amphiphilic covalent organic framework material according to claim 2 or 3, characterized in that, The catalyst described in step 1 is glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoic acid, concentrated hydrochloric acid with a mass percentage concentration of 30% - 37% or concentrated sulfuric acid with a mass percentage concentration of 95% - 98%.

5. The preparation method of an amphiphilic covalent organic framework material according to claim 2 or 3, characterized in that, The sulfonic diamine described in step 1 is 2,5-diaminobenzene-1,4-disulfonic acid or 2,5-diaminobenzenesulfonic acid.

6. The preparation method of an amphiphilic covalent organic framework material according to claim 2 or 3, characterized in that, The phenanthroimidazole diamine described in step 1 is 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine or 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine.

7. The preparation method of an amphiphilic covalent organic framework material according to claim 6, characterized in that, The synthesis method of 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine (NH2-PIP-C8) is as follows: (1) First, react concentrated HNO3 with a mass percentage concentration of 63% - 65%, concentrated H2SO4 with a mass percentage concentration of 95% - 98% and 9,10-phenanthrenequinone at 80 - 150 °C for 12 - 96 hours to obtain a pale yellow solid 2,7-dinitro-9,10-phenanthrenequinone; (2) Then react 2,7-dinitro-9,10-phenanthrenequinone, ammonium acetate and 4-n-octyloxybenzaldehyde to obtain 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro; (3) Then add 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro and 2,7-dinitro-9,10-phenanthrenequinone into hydrazine hydrate and react at 60 - 120 °C for 12 - 36 hours to obtain 2-[4-(octyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine.

8. The preparation method of an amphiphilic covalent organic framework material according to claim 6, characterized in that, The synthesis method of 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine is as follows: (1) First, concentrated HNO3 with a mass percentage concentration of 63% - 65%, concentrated H2SO4 with a mass percentage concentration of 95% - 98%, and 9,10-phenanthrenequinone are reacted at 80 - 150 °C for 12 - 96 hours to obtain light yellow solid 2,7-dinitro-9,10-phenanthrenequinone; (2) Then, 2,7-dinitro-9,10-phenanthrenequinone, ammonium acetate, and 4-n-dodecyloxybenzaldehyde are reacted to obtain 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro; (3) Then, 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-dinitro and 2,7-dinitro-9,10-phenanthrenequinone are added to hydrazine hydrate and reacted at 60 - 120 °C for 12 - 36 hours to obtain 2-[4-(dodecyloxy)phenyl]-1H-phenanthro[9,10-d]imidazole-5,10-diamine.

9. The preparation method of an amphiphilic covalent organic framework material according to claim 2 or 3, characterized in that, The organic solvent II described in step four is one or a combination of two of acetone, ethanol, methanol, tetrahydrofuran, ethyl acetate, dichloromethane, or 1,2-dichloroethane.

10. Use of an amphiphilic covalent organic framework material according to claim 1, characterized in that, This application uses the amphiphilic covalent organic framework material as an emulsifier for oil-water two-phase emulsification.

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