An acid-functionalized cofs polymer material and preparation method and application thereof

Abstract

The application belongs to the technical field of heterogeneous catalysis, and particularly relates to an acid functionalized COFs polymer material, a preparation method and application thereof. A p-toluenesulfonic acid monohydrate and 2,5-diaminobenzenesulfonic acid are uniformly mixed by grinding in a mortar for 5 min, a tricarbonyl phloroglucinol is added and uniformly mixed by continuing to grind for 10 min, then distilled water is added and continues to grind for 20 min; after the mixture after grinding is heated by programmed temperature heating reaction and cooled to room temperature, the product is washed and vacuum dried to obtain the acid functionalized COFs polymer material. The application is prepared by using 2,5-diaminobenzenesulfonic acid and tricarbonyl phloroglucinol as reactants, and a typical Schiff base reaction is used to prepare the acid functionalized COFs polymer material in a short time, and the preparation method is simple and efficient.

Description

Technical Field

[0001] The present invention belongs to the technical field of heterogeneous catalysis, and in particular relates to an acid-functionalized COFs polymer material and a preparation method and application thereof. Background Art

[0002] In the context of environmental pollution and energy shortage, it is crucial for diesel engines to reduce the emission of harmful substances such as particulate matter and nitrogen oxides. n Polymethoxydialkyl ethers (PMEs) are attracting widespread attention as a new, green, clean diesel additive. Without modifying the diesel engine, PMEs can be mixed with diesel to form a blended fuel. The use of blended fuels significantly reduces exhaust emissions while improving the combustion efficiency of internal combustion engines, which is of great significance to environmental protection and sustainable development.

[0003] The synthesis of polymethoxydialkyl ethers is an acid-catalyzed reaction, and the design and preparation of catalysts has always been a hot topic and a difficult problem in research. Traditional liquid acid catalysts have certain reaction activity, but they have disadvantages such as being corrosive, difficult to separate, and harmful to the environment. Compared with traditional liquid acids, solid acid catalysts have many advantages such as easy separation and reusability. However, for polymethoxydiethyl ethers (DEMs) with long chain groups, the design and preparation of catalysts have always been a hot topic and a difficult problem in research. n , 2≤n≤8), the research on solid acid catalysts is still very limited. Summary of the Invention

[0004] The purpose of the present invention is to provide an acid-functionalized COFs polymer material and a preparation method and application thereof to solve the above technical problems.

[0005] In order to achieve the above technical objectives, the technical solution of the present invention is:

[0006] A method for preparing an acid-functionalized COFs polymer material comprises grinding p-toluenesulfonic acid monohydrate and 2,5-diaminobenzenesulfonic acid in a mortar for 5 minutes to mix evenly, adding trialdehyde phloroglucinol and continuing to grind for 10 minutes to mix evenly, then adding distilled water and continuing to grind for 20 minutes; the ground mixture is subjected to a programmed temperature heating reaction, cooled to room temperature after the reaction is completed, and the product is washed and vacuum dried to obtain the acid-functionalized COFs polymer material.

[0007] As a further improvement, the molar ratio of the 2,5-diaminobenzenesulfonic acid to trialdehyde phloroglucinol is 3:2, and the molar ratio of p-toluenesulfonic acid monohydrate to 2,5-diaminobenzenesulfonic acid is 5-6:1.

[0008] As a further improvement, the amount of distilled water added is 0.2-0.3 mL.

[0009] As a further improvement, the programmed temperature increase is as follows: first increase the temperature to 60°C and heat the reaction for 6-8 hours, then increase the temperature to 90°C and heat the reaction for 10-12 hours.

[0010] The present invention also provides an acid-functionalized COFs polymer material, the structural formula of the acid-functionalized COFs polymer material is:

[0011] .

[0012] The present invention also provides an application of an acid-functionalized COFs polymer material in the preparation of polymethoxydiethyl ether. Diethoxymethane, trioxymethylene and the acid-functionalized COFs polymer material are uniformly mixed and reacted at 40-70°C and normal pressure for 30-240 minutes to obtain polymethoxydiethyl ether.

[0013] As a further improvement, the amount of the acid-functionalized COFs polymer material is 1-5% of the total mass of diethoxymethane and trioxymethylene.

[0014] Due to the adoption of the above technical solution, the present invention has the following beneficial effects:

[0015] The present invention provides a method for preparing an acid-functionalized COFs polymer material. The material is prepared in a short time by simply grinding the reactants and utilizing a typical Schiff base reaction. The preparation method is simple and efficient.

[0016] The acid-functionalized COFs polymer catalyst prepared by the present invention has the advantages of certain crystallinity, large specific surface area, rich pore structure, high acid strength, good chemical stability, etc. It is used as a catalyst for acetalization reaction, especially the preparation of polymethoxydiethyl ether, and shows excellent catalytic performance. It does not require high temperature and high pressure conditions and can selectively synthesize polymethoxydiethyl ether DEM. 2-8 , the product is polyoxyethylene diethyl ether DEM 2-8 The selectivity is over 90%. Moreover, under mild reaction conditions, the catalytic performance of acid-functionalized COFs polymer materials is significantly better than that of common solid acid catalysts such as molecular sieves, acidic resins, and p-toluenesulfonic acid.

[0017] The present invention utilizes the characteristics of covalent organic framework compounds (COFs) that can be pre-designed, controllably synthesized, and have adjustable functions to design and synthesize new functional porous polymer materials. The functionalized COFs materials are innovatively used as solid acid catalysts and applied to the synthesis reaction of polymethoxydiethyl ether, showing excellent catalytic performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1The SEM images and mapping images of Tp-DABA-SO3H COFs prepared in Example 1 are shown, wherein a is the SEM image of Tp-DABA-SO3H COFs, and b is the mapping image of Tp-DABA-SO3H COFs;

[0019] Figure 2 is a TEM image of Tp-DABA-SO3H COFs prepared in Example 1;

[0020] Figure 3 is the XRD pattern of Tp-DABA-SO3H COFs prepared in Example 1;

[0021] Figure 4 is the infrared spectrum of Tp-DABA-SO3H COFs prepared in Example 1;

[0022] Figure 5 is the nitrogen physical adsorption-desorption isotherm curve of Tp-DABA-SO3H COFs prepared in Example 1;

[0023] Figure 6 is the pore size distribution diagram of Tp-DABA-SO3H COFs prepared in Example 1;

[0024] Figure 7 This is the thermogravimetric spectrum of Tp-DABA-SO3H COFs prepared in Example 1;

[0025] Figure 8 This is the NH3-TPD spectrum of Tp-DABA-SO3H COFs prepared in Example 1;

[0026] Figure 9 This is the gas chromatography analysis spectrum of Example 4;

[0027] Figure 10 This is the gas chromatography analysis spectrum of Example 5;

[0028] Figure 11 This is the gas chromatography analysis spectrum of Example 6;

[0029] Figure 12 This is the gas chromatography analysis spectrum of Example 7;

[0030] Figure 13 This is the gas chromatography analysis spectrum of Example 8;

[0031] Figure 14 This is the gas chromatography analysis spectrum of Example 9;

[0032] Figure 15 This is the gas chromatography analysis spectrum of Example 10;

[0033] Figure 16 This is the gas chromatography analysis spectrum of Example 11;

[0034] Figure 17 This is the gas chromatography analysis spectrum of Example 12;

[0035] Figure 18 This is a gas chromatography analysis spectrum of Comparative Example 1;

[0036] Figure 19 This is a gas chromatography analysis spectrum of Comparative Example 2;

[0037] Figure 20 This is the gas chromatography analysis spectrum of Comparative Example 3. DETAILED DESCRIPTION

[0038] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of 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 premise belong to the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0039] The acid-functionalized COFs polymer material of the present invention is a covalent organic framework compound (COFs).

[0040] Example 1 An acid-functionalized COFs polymer material has the following structural formula:

[0041] .

[0042] This embodiment also provides a preparation method of the acid-functionalized COFs polymer material, which specifically comprises the following steps: grinding 1.3005 g of p-toluenesulfonic acid monohydrate (PTSA) and 0.2630 g of 2,5-diaminobenzenesulfonic acid (DABA) in an agate mortar for 5 minutes at room temperature until uniformly mixed, wherein the molar ratio of the catalyst p-toluenesulfonic acid monohydrate (PTSA) to 2,5-diaminobenzenesulfonic acid (DABA) during the grinding process is 5:1, then adding 0.1956 g of the reactant trialdehyde phloroglucinol (Tp), and continuing to grind for 10 minutes to mix uniformly, wherein the molar ratio of the reactant 2,5-diaminobenzenesulfonic acid (DABA) to trialdehyde phloroglucinol (Tp) is 3:2, and then slowly adding 0.25 g of pyroxenesulfonic acid to the mortar. L distilled water, continue grinding for 20 minutes to obtain a uniform mixture, and the mixture after grinding is subjected to a programmed temperature heating reaction, first heated at 60°C for 6 hours, and then heated at 90°C for 12 hours. After the reaction is completed, the product is cooled to room temperature, washed with distilled water 6 times, and then centrifuged and washed 3 times with N,N-dimethylacetamide, tetrahydrofuran, and anhydrous ethanol in sequence. The washed product is vacuum dried at 90°C for 12 hours to obtain an acid-functionalized COFs polymer material, named Tp-DABA-SO3H COFs polymer material.

[0043] The preparation equation of Tp-DABA-SO3H COFs polymer material is as follows:

[0044] .

[0045] like Figure 1 As shown in the figure, the scanning electron microscope (SEM) image and mapping image of the Tp-DABA-SO3H COFs polymer material prepared in this embodiment are shown, wherein a is a scanning electron microscope (SEM) image of the polymer material, and b is a mapping image of the polymer. It can be seen from Figure a that the prepared Tp-DABA-SO3H COFs polymer material presents a morphology of irregular flakes stacked into blocks, and Figure b shows that the catalyst contains C, N, O, and S elements, which are relatively evenly distributed.

[0046] like Figure 2 The figure shows the transmission electron microscope (TEM) image of the Tp-DABA-SO3H COFs polymer material prepared in this example. It can be seen that the Tp-DABA-SO3H COFs polymer material has a sheet-like structure and contains a certain pore structure.

[0047] like Figure 3As shown in Figure 1, this is the XRD spectrum of the Tp-DABA-SO3H COFs polymer material prepared in this example. It can be seen that the Tp-DABA-SO3H COFs polymer material has a sharp peak at 4.7°, corresponding to the (100) crystal plane of the COFs polymer, and a wider peak at 26.5°, which may be caused by the defects of π-π bond stacking between continuous COFs layers.

[0048] like Figure 4 As shown in the figure, it is the infrared spectrum of the Tp-DABA-SO3H COFs polymer material prepared in this example. It can be seen that the Tp-DABA-SO3H COFs polymer material has an infrared spectrum of 1438 cm -1 、1080cm -1 and 1026cm -1 The strong peak at is considered to be related to the O=S=O symmetric and asymmetric stretching vibrations of the -SO3H group, indicating that the prepared COFs polymer material contains -SO3H groups.

[0049] like Figure 5 As shown in FIG, the nitrogen physical adsorption-desorption isotherm curve of the Tp-DABA-SO3H COFs polymer material prepared in this embodiment shows that the Tp-DABA-SO3H COFs polymer material presents a typical type IV isotherm, has a mesoporous structure, a specific surface area of ​​209, has a large specific surface area, and has a rich pore structure.

[0050] like Figure 6 As shown in FIG. 1 , it is a pore size distribution diagram of the Tp-DABA-SO 3 H COFs polymer material prepared in this example. It can be seen that the pore sizes of the Tp-DABA-SO 3 H COFs polymer material are mainly distributed in 3-5 nm and 10-48 nm.

[0051] like Figure 7 As shown in FIG, the thermogravimetric spectrum of the Tp-DABA-SO3H COFs polymer material prepared in this embodiment can be seen. It can be seen that the Tp-DABA-SO3H COFs polymer material can maintain 82% of its mass at about 250°C, indicating that the Tp-DABA-SO3H COFs polymer material has good thermal stability.

[0052] like Figure 8 As shown in FIG. 1 , the NH3-TPD spectrum of the Tp-DABA-SO3H COFs polymer material prepared in this example shows a large NH3 desorption peak at around 130° C. The acid content of the catalyst was calculated based on the peak area, which was 0.82 mmol / g.

[0053] Example 2 This example provides a method for preparing an acid-functionalized COFs polymer material, specifically: 1.5606 g of p-toluenesulfonic acid monohydrate (PTSA) and 0.2630 g of 2,5-diaminobenzenesulfonic acid (DABA) were ground in an agate mortar at room temperature for 5 minutes to mix evenly, the molar ratio of the catalyst p-toluenesulfonic acid monohydrate (PTSA) and 2,5-diaminobenzenesulfonic acid (DABA) during the grinding process was 6:1, and then 0.1956 g of the reactant trialdehyde phloroglucinol (Tp) was added, and the grinding was continued for 10 minutes to mix evenly, the molar ratio of the reactant 2,5-diaminobenzenesulfonic acid (DABA) and trialdehyde phloroglucinol (Tp) was 3:2, and then slowly added to the mortar. 0.2 mL of distilled water was slowly added dropwise, and grinding was continued for 20 min to obtain a uniformly mixed mixture. The mixture after grinding was subjected to a programmed temperature heating reaction, first heated at 60 ° C for 8 h, and then heated at 90 ° C for 10 h. After the reaction, the product was cooled to room temperature, washed with distilled water 6 times, and then centrifuged and washed 3 times with N, N-dimethylacetamide, tetrahydrofuran, and anhydrous ethanol in sequence. The washed product was vacuum dried at 90 ° C for 12 h to obtain an acid-functionalized COFs polymer material.

[0054] Example 3 This example provides a method for preparing an acid-functionalized COFs polymer material, specifically: 1.4306 g of p-toluenesulfonic acid monohydrate (PTSA) and 0.2630 g of 2,5-diaminobenzenesulfonic acid (DABA) were ground in an agate mortar at room temperature for 5 minutes to mix evenly, and the molar ratio of the catalyst p-toluenesulfonic acid monohydrate (PTSA) and 2,5-diaminobenzenesulfonic acid (DABA) during the grinding process was 5.5:1. Then, 0.1956 g of the reactant trialdehyde phloroglucinol (Tp) was added, and the grinding was continued for 10 minutes to mix evenly, and the molar ratio of the reactant 2,5-diaminobenzenesulfonic acid (DABA) and trialdehyde phloroglucinol (Tp) was 3:2. Then, the mixture was added to the mortar. 0.3 mL of distilled water was slowly added dropwise and grinding was continued for 20 min to obtain a uniformly mixed mixture. The mixture after grinding was subjected to a programmed temperature heating reaction, first heated at 60 ° C for 7 h, and then heated at 90 ° C for 11 h. After the reaction, the product was cooled to room temperature, washed with distilled water 6 times, and then centrifuged and washed 3 times with N, N-dimethylacetamide, tetrahydrofuran, and anhydrous ethanol in sequence. The washed product was vacuum dried at 90 ° C for 12 h to obtain an acid-functionalized COFs polymer material.

[0055] Example 4 In this example, the acid-functionalized COFs polymer material prepared in Example 1 was used as a catalyst to prepare polyoxyethylene diethyl ether. The specific method was as follows: 1.0600 g of diethoxymethane and 0.5402 g of trioxymethylene were added to the reactor, and 0.0800 g of the acid-functionalized COFs polymer catalyst was added. The reaction was carried out at 40°C and normal pressure for 2 h. After the reaction was completed, the product was cooled to room temperature and subjected to chromatographic analysis. The chromatographic analysis spectrum is shown as follows: Figure 9 As shown. Analysis found that the conversion rate of the reactant trioxymethylene was 18.22%, and the product polyoxyethylene diethyl ether DEM 2-8 The selectivity is 92.18%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity is 16.64%.

[0056] The peak order of the reaction products is: ethanol (retention time: 3.50 min), tetrahydrofuran (retention time: 4.80 min), reactant DEM (retention time: 5.37 min), reactant TOX (retention time: 5.63 min), reaction product DEM2 (retention time: 8.45 min), reaction product DEM3 (retention time: 10.71 min), reaction product DEM4 (retention time: 12.36 min), reaction product DEM5 (retention time: 13.71 min), reaction product DEM6 (retention time: 15.04 min), reaction product DEM7 (retention time: 16.61 min), reaction product DEM8 (retention time: 18.76 min). The chromatogram is shown in FIG. Figure 9 shown.

[0057] Example 5 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0800g of an acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 50°C and normal pressure for 2h. After the reaction is completed, the mixture is cooled to room temperature, and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 10 As shown. Analysis found that the conversion rate of the reactant trioxymethylene was 55.59%, and the product polyoxyethylene diethyl ether DEM 2-8 The selectivity is 96.41%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity is 46.93%.

[0058] Example 6 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0800g of an acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 60°C and normal pressure for 2h. After the reaction is completed, the mixture is cooled to room temperature, and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 11Analysis showed that the conversion rate of the reactant trioxymethylene was 92.40%, and the product polyoxyethylene diethyl ether DEM was 2-8 The selectivity is 97.35%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity was 63.40%, and the product distribution conformed to the Schulz-Flory distribution.

[0059] Example 7 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0800g of an acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 70°C and normal pressure for 2h. After the reaction is completed, the mixture is cooled to room temperature, and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 12 As shown. Analysis found that the conversion rate of the reactant trioxymethylene was 92.44%, and the product polyoxyethylene diethyl ether DEM 2-8 The selectivity is 98.78%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity is 63.50%.

[0060] Example 8 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0800g of acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 60°C and normal pressure for 30min. After the reaction is completed, the mixture is cooled to room temperature, and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 13 Analysis showed that the conversion rate of the reactant trioxymethylene was 53.60%, and the product polyoxyethylene diethyl ether DEM was 2-8 The selectivity is 95.86%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity is 46.69%.

[0061] Example 9 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0800g of an acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 60°C and normal pressure for 1h. After the reaction is completed, the mixture is cooled to room temperature, and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 14 As shown. Analysis found that the conversion rate of the reactant trioxymethylene was 77.20%, and the product polyoxyethylene diethyl ether DEM 2-8 The selectivity is 97.45%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity is 60.17%.

[0062] Example 10 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0800g of an acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 60°C and normal pressure for 4h. After the reaction is completed, the mixture is cooled to room temperature, and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 15 As shown. Analysis found that the conversion rate of the reactant trioxymethylene was 93.88%, and the product polyoxyethylene diethyl ether DEM 2-8 The selectivity is 97.64%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity is 62.79%.

[0063] Example 11 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0162g of an acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 60°C and normal pressure for 2h. After the reaction is completed, the mixture is cooled to room temperature, and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 16 Analysis showed that the conversion rate of the reactant trioxymethylene was 38.10%, and the product polyoxyethylene diethyl ether DEM was 38.10%. 2-7 The selectivity is 96.74%, and the product is polyoxyethylene diethyl ether DEM 3-7 The selectivity is 41.42%.

[0064] Example 12 This example provides another method for preparing polymethoxydiethyl ether, specifically: 1.0600g of diethoxymethane and 0.5402g of trioxymethylene are added to a reactor, 0.0482g of acid-functionalized COFs polymer catalyst is added, and the mixture is reacted at 60°C and normal pressure for 2h. After the reaction is completed, the mixture is cooled to room temperature and the product is subjected to chromatographic analysis. The analysis spectrum is as shown below. Figure 17 Analysis showed that the conversion rate of the reactant trioxymethylene was 81.46%, and the product polyoxyethylene diethyl ether DEM was 81.46%. 2-8 The selectivity is 97.37%, and the product is polyoxyethylene diethyl ether DEM 3-8 The selectivity is 61.80%.

[0065] Comparative Example 1 This comparative example provides a preparation method of polymethoxydiethyl ether. The specific preparation method is the same as that of Example 6, except that in this comparative example, the catalyst acid-functionalized COFs polymer is replaced with H-ZSM-35 molecular sieve material. The amount of H-ZSM-35 molecular sieve material is 0.0800 g. The obtained product is subjected to chromatographic analysis, and the analysis spectrum is as follows: Figure 18 As shown in the figure, the conversion rate of the reactant trioxymethylene is only 2.70%, and the only reaction product is polyoxyethylene diethyl ether DEM2.

[0066] Comparative Example 2 This comparative example provides a method for preparing polymethoxydiethyl ether. The specific preparation method is the same as that in Example 6, except that in this comparative example, the catalyst acid-functionalized COFs polymer is replaced with Amberlite-732 resin, and the amount of Amberlite-732 resin used is 0.0800 g. The obtained product is subjected to chromatographic analysis, and the analysis spectrum is as follows: Figure 19 The conversion rate of the reactant trioxymethylene was only 1.32%, and only a small amount of polyoxyethylene diethyl ether DEM2 was generated as the reaction product.

[0067] Comparative Example 3 This comparative example provides a method for preparing polymethoxydiethyl ether. The specific preparation method is the same as that in Example 6, except that in this comparative example, the catalyst acid functionalized COFs polymer is replaced with p-toluenesulfonic acid, and the amount of p-toluenesulfonic acid used is 0.0800 g. The obtained product is subjected to chromatographic analysis, and the analysis spectrum is as follows: Figure 20 As shown in the figure, the conversion rate of the reactant trioxymethylene is only 3.60%, and the only reaction product is polyoxyethylene diethyl ether DEM2.

[0068] By comparing the conversion rate of the reactants and the selectivity of the products in Examples 4-7, it was found that under the reaction temperature of 50~70°C, the conversion rate of the reactants was high, all above 50%; by comparing Example 6 and Examples 8-10, it was found that the reaction time was 30~240min, and the conversion rate was good, all above 50%; by comparing Example 6 and Examples 11-12, it was found that when the amount of catalyst acid-functionalized COFs polymer was 3~5%, the system had a good conversion rate, above 80%.

[0069] By comparing Example 6 with Comparative Examples 1-3, it is found that the acid-functionalized COFs polymer prepared by the present invention has good catalytic performance as a catalyst in the preparation of polymethoxydiethyl ether, and the conversion rate of the reactants is much higher than that of solid acid catalysts such as molecular sieve materials and resin materials.

[0070] In the present invention, the gas chromatography analysis conditions are:

[0071] The chromatographic column is a SE-54 column with a size of 60 m × 0.25 mm × 0.25 mm;

[0072] The programmed temperature conditions were as follows: initial temperature 60°C, hold for 4.5 min, run for 4.5 min, increase to 260°C at 20°C / min, hold for 8 min, and run time of 22.5 min;

[0073] The injection port temperature was 300°C; the injection volume was 1 μL; the carrier gas was high-purity nitrogen; the column flow rate was 2.0 mL / min; the purge flow rate was 5.0 mL / min; the split mode was Split; the FID detector temperature was 300°C, and the column oven temperature was 60°C.

[0074] The specific embodiments of the present invention described above do not limit the scope of protection of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. Application of an acid-functionalized COFs polymer material in the preparation of polymethoxydiethyl ether, characterized in that: Diethoxymethane, trioxymethane and acid-functionalized COFs polymer material were mixed uniformly and reacted at 40-70°C and normal pressure for 30-240 minutes to prepare polyoxyethylene diethyl ether. The preparation method of the acid-functionalized COFs polymer material comprises: grinding p-toluenesulfonic acid monohydrate and 2,5-diaminobenzenesulfonic acid in a mortar for 5 minutes to mix evenly, adding trialdehyde phloroglucinol and continuing to grind for 10 minutes to mix evenly, then adding distilled water and continuing to grind for 20 minutes; heating the ground mixture to a programmed temperature for reaction, cooling to room temperature after the reaction, washing the product and vacuum drying to obtain the acid-functionalized COFs polymer material; The molar ratio of 2,5-diaminobenzenesulfonic acid to trialdehyde phloroglucinol is 3:2, and the molar ratio of p-toluenesulfonic acid monohydrate to 2,5-diaminobenzenesulfonic acid is 5-6:1; The amount of distilled water added is 0.2~0.3mL; The specific temperature program is as follows: first heat to 60°C and heat to react for 6-8 hours, then heat to 90°C and heat to react for 10-12 hours.

2. The use of the acid-functionalized COFs polymer material according to claim 1 in the preparation of polymethoxydiethyl ether, characterized in that: The amount of the acid-functionalized COFs polymer material is 1-5% of the total mass of diethoxymethane and trioxymethylene.

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