Thiazole group-containing polyphenyl structure conjugated microporous polymer and preparation method thereof

Abstract

The invention relates to a bipolyphenyl structure conjugated microporous polymer containing a thiazole group and a preparation method thereof, and belongs to the technical field of organic porous materials, the process comprises the following steps: carrying out a coupling reaction to synthesize two conjugated microporous polymers containing the thiazole group, namely CMP-TBB-BBT and CMP-TBQ-BBT, by taking TBB or (TBQ and BBT) as monomers, carrying out a reaction to synthesize CMP-TBB-BBT and CMP-TBQ-BBT, taking 4-bromoacetophenone as a monomer, taking TBQ as 4-(2-bromophenyl) acetophenone as a monomer, and carrying out a reaction to synthesize CMP-TBQ-BBT and CMP-TBQ-BBT; the method is simple to operate, and has the characteristics of mild reaction conditions, low synthesis cost, high product yield and the like. Structural characterization is carried out on the target product through modern analysis methods such as SEM, solid < 13 > C NMR and FT-IR spectral analysis, characterization results determine that the product is the CMPs material containing the thiazole group, and the application range is wide.

Description

Technical Field

[0001] The invention relates to the technical field of synthesis of organic porous polymer materials, in particular to two bipolyphenyl structure conjugated microporous polymers containing thiazole groups and preparation methods thereof. Background Art

[0002] In recent years, new two-dimensional covalent organic framework materials (2D CMPs) have shown good application prospects in the field of organic semiconductor photocatalysis. They have the characteristics of high specific surface area, adjustable pores, easy functionalization and highly dispersed catalytic active sites, which are conducive to the contact between substrates and catalytic active sites. They are ideal catalysts and have shown great application potential in the field of photocatalysis, which has attracted widespread attention from researchers. However, there are still deficiencies in the application research of two-dimensional covalent organic framework materials, which need to be continuously explored.

[0003] The thiazole group has a rigid planar molecular configuration. The presence of thiazole groups in covalent organic framework materials is conducive to the orderly arrangement of molecules and improves the crystallinity of the material. In addition, this orderly stacking of molecules formed by π-π interactions can not only broaden the spectral absorption range and promote interlayer electron delocalization, but also provide necessary channels for the interlayer transmission of photogenerated charges, which helps to separate and transfer photogenerated charges, indicating the outstanding advantages of covalent organic framework materials containing thiazole groups in photocatalysis.

[0004] The existing technologies for synthesizing CMP-TBB-BBT and CMP-TBQ-BBT have problems such as long reaction cycle, low yield, high cost, and complicated process steps, which seriously restrict the development and application of the conjugated microporous polymer materials. Summary of the invention

[0005] In view of the problems of high cost, complicated preparation process, low yield, poor purity and the like in the current synthesis of CMP-TBB-BBT and CMP-TBQ-BBT, the technical purpose of the present invention is to provide a method for synthesizing two conjugated microporous polymers with biphenyl structures containing thiazole groups. The process starts from designing and synthesizing nitrogen- and sulfur-containing thiazole group building units, generates carbon-carbon single bonds through substitution reaction coupling, and finally constructs them into adsorption-type conjugated microporous polymers with biphenyl structures containing thiazole groups. The process has the advantages of simple preparation method, high yield, low cost, and environmental friendliness. The prepared conjugated microporous polymers have the characteristics of large specific surface area, wide application, good adsorption prospects, and the like, and have a wide range of applications.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is: A conjugated microporous polymer having a bipolyphenyl structure and containing a thiazole group, wherein the structural formula of the conjugated microporous polymer is:

[0007] The preparation method of the bipolyphenyl structure conjugated microporous polymer containing thiazole groups comprises the following steps: Step 1, weighing silicon tetrachloride and 4-(2-bromophenyl)acetophenone or 4-bromoacetophenone in a molar ratio of (1-3):1, then dissolving the weighed 4-(2-bromophenyl)acetophenone or 4-bromoacetophenone in anhydrous ethanol, and after it is completely dissolved, adding the weighed silicon tetrachloride dropwise thereto, and carrying out a mixing reaction under continuous stirring for 10-14 hours, then adding a saturated ammonium chloride solution (at least 250 ml) to the obtained mixture, mixing it thoroughly, and then subjecting it to rotary evaporation at 40-60° C., then first extracting the remaining product after rotary evaporation with dichloromethane, and then separating it with a developing agent by column chromatography to obtain a primary product, then removing the developing agent in the primary product by rotary evaporation, and vacuum drying it at 95-105° C. to obtain 1,3,5-tris(4-bromo-1,1'-biphenyl-4'-yl)benzene or 1,3,5-tris(4-bromophenyl)benzene for standby use; Step 2: Weigh 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole and 1,3,5-tri(4-bromo-1,1'-biphenyl-4'-yl)benzene or 1,3,5-tri(4-bromophenyl)benzene prepared in step 1 in a molar ratio of (1-3):1, then weigh the weighed 1,3,5-tri(4-bromo-1,1'-biphenyl-4'-yl)benzene or 1 ,3,5-tri(4-bromophenyl)benzene is placed in a pressure-resistant container, and then 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole, anhydrous N,N'-dimethylformamide, anhydrous potassium carbonate and tetrakis(triphenylphosphine)palladium are added thereto. Under the conditions of inert gas protection and continuous stirring, the pressure-resistant tube is placed in a temperature environment of 120-200°C for reaction for 24-72h; Step 3: After the reaction is completed and the product is cooled, the obtained reaction product is washed with N,N'-dimethylformamide, filtered, and then washed with distilled water to remove N,N'-dimethylformamide. After filtering again, it is washed with ethanol, then filtered, and then placed in a vacuum drying environment at a temperature of 95-105°C for 10-24h. After grinding, a bright yellow powder target product CMP-TBQ-BBT or CMP-TBB-BBT is obtained.

[0008] Furthermore, in step 1, the molar ratio of the 4-(2-bromophenyl)acetophenone or 4-bromoacetophenone to silicon tetrachloride is 1:3.

[0009] Furthermore, in step 1, the developing solvent used for column chromatography separation is a mixed solvent of dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether in the mixed solvent is 1:1.

[0010] Furthermore, in step 1, the addition ratio of the 4-(2-bromophenyl)acetophenone or 4-bromoacetophenone to anhydrous ethanol is 0.9-1.2 mol / L.

[0011] Furthermore, in step 1, the mixing reaction time of 4-(2-bromophenyl)acetophenone or 4-bromoacetophenone and silicon tetrachloride is 12 hours.

[0012] Furthermore, in step 2, the molar ratio of 1,3,5-tri(4-bromo-1,1'-biphenyl-4'-yl)benzene or 1,3,5-tri(4-bromophenyl)benzene to 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-2,1,3-benzothiadiazole is 2:3.

[0013] Furthermore, in step 2, the mass ratio of the added anhydrous N,N'-dimethylformamide, anhydrous potassium carbonate and tetrakis(triphenylphosphine)palladium is 9:24:4.

[0014] Furthermore, in step 2, the inert gas is nitrogen, and the pressure container is filled with nitrogen for no less than 5 minutes, the reaction temperature is 150° C., and the reaction time is 48 hours.

[0015] Furthermore, in step 1 and step 2, the stirring speed is 200 r / min.

[0016] Beneficial effects: The preparation process of the present invention first uses 4-bromoacetophenone or 4-(2-bromophenyl)acetophenone as a monomer and silicon tetrachloride as a catalyst to prepare TBB or TBQ through a substitution reaction. This step has the advantages of low raw material cost, mild reaction conditions, simple process operation, high product yield, etc. through the reasonable selection of reaction raw materials and catalysts, and precise regulation of process parameters during the reaction process; then, TBB or TBQ and BBT are used as reaction raw material monomers, N,N'-dimethylformamide is used as a solvent, and tetrakis(triphenylphosphine)palladium is used as a catalyst to prepare two thiazole-containing polyphenyl structure conjugated microporous polymers (CMP-TBB-BBT, CMP-TBQ-BBT) through a synthetic reaction. The process method itself has the advantages of novel raw material structure, simple synthesis process, convenient operation, low cost, high finished product yield, mild reaction conditions, and low environmental pollution. The synthesized CMP-TBB-BBT and CMP-TBQ-BBT have the characteristics of large specific surface area, wide application, good adsorption prospects, etc., and have potential application prospects in the fields of photocatalysis and optoelectronics. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The synthetic route of TBB molecule synthesized by the present invention; Figure 2 The synthetic route of the CMP-TBB-BBT material synthesized in the present invention; Figure 3 The structure diagram of the CMP-TBB-BBT material synthesized by the present invention; Figure 4 The hydrogen nuclear magnetic resonance spectrum of the TBB material synthesized by the present invention; Figure 5 The carbon nuclear magnetic resonance spectrum of the TBB material synthesized by the present invention; Figure 6 This is a scanning electron microscope image of the CMP-TBB-BBT material synthesized by the present invention; Figure 7 This is a scanning electron microscope magnified image of the CMP-TBB-BBT material synthesized by the present invention; Figure 8 This is the infrared spectrum of the CMP-TBB-BBT material synthesized by the present invention; Fig. 9 The synthetic route of the TBQ molecule synthesized by the present invention; Fig.10 The synthetic route of the CMP-TBQ-BBT material synthesized by the present invention; Fig.11 The structure diagram of the CMP-TBQ-BBT material synthesized in the present invention; Fig.12 The hydrogen nuclear magnetic resonance spectrum of the TBQ material synthesized by the present invention; Fig.13 The carbon nuclear magnetic resonance spectrum of the TBQ material synthesized by the present invention; Fig.14 This is a scanning electron microscope image of the CMP-TBQ-BBT material synthesized by the present invention; Fig.15 This is a scanning electron microscope magnified image of the CMP-TBQ-BBT material synthesized by the present invention; Fig.16 This is the infrared spectrum of the CMP-TBQ-BBT material synthesized in the present invention. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments: The present invention provides two biphenyl structure conjugated microporous polymers containing thiazole groups and a synthesis method thereof. The synthesis principles of the two biphenyl structure conjugated microporous polymers containing thiazole groups are the same and are both divided into two steps of synthesis: The first step is the synthesis of TBB and TBQ The synthesis of TBB is as follows: according to the molar ratio of 4-bromoacetophenone to silicon tetrachloride of 1: (1-3), 4-bromoacetophenone is placed in a 100ml round-bottom flask, 6ml of anhydrous ethanol is taken using a pipette to dissolve the above solid, and silicon tetrachloride is slowly added to the solution at room temperature using a pipette to react for 12h. After the reaction is completed, 250ml of saturated ammonium chloride solution is added to the flask, and then rotary evaporation is performed at 40-60°C, followed by extraction with dichloromethane, and after rotary evaporation of the extracted organic matter, the target product is obtained by column chromatography, and then the developing agent is rotary evaporated, and vacuum drying is performed at 100°C for 10-24h to obtain 1,3,5-tri(4-bromophenyl)benzene (TBB).

[0019] The synthetic formula of TBB is as follows: The synthesis of TBQ is as follows: according to the molar ratio of 4-(2-bromophenyl)acetophenone to silicon tetrachloride of 1:(1-3), 4-(2-bromophenyl)acetophenone is placed in a 100ml round-bottom flask, 6ml of anhydrous ethanol is taken using a pipette to dissolve the above solid, and silicon tetrachloride is slowly added to the solution using a pipette at room temperature for 12h. After the reaction is completed, a small amount of saturated ammonium chloride solution is added to the flask, and then rotary evaporation is performed at 40-60°C, followed by extraction with dichloromethane, and the extracted organic matter is rotary evaporated, and the target product is obtained by column chromatography, and then the developing agent is rotary evaporated, and vacuum drying is performed at 100°C for 10-24h to obtain 1,3,5-tri(4-bromo-1,1'-biphenyl-4'-yl)benzene (TBQ). The synthetic formula of TBQ is as follows: The second step is the synthesis of CMP-TBB-BBT and CMP-TBQ-BBT The synthesis of CMP-TBB-BBT is: According to the molar ratio of TBB to BBT being 1:(1-3), TBB is placed in a 35 ml pressure tube, and then 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (BBT), 9 ml of anhydrous DMF, 249 mg of anhydrous potassium carbonate and 4 mg of tetrakis(triphenylphosphine)palladium are added thereto, and then nitrogen is filled into the pressure tube, and the pressure tube is placed at a temperature of 120-200° C. to react for 24-72 hours. After the reaction is completed, the product is cooled, dispersed in DMF, unreacted raw materials are washed away, filtered, and then DMF is washed away with secondary distilled water, filtered, and then anhydrous ethanol is used to fully stir, wash and filter. After filtering, it is vacuum dried at 100° C. for 10-24 hours. The bright yellow powder obtained after grinding is the target product CMP-TBB-BBT. The synthetic formula of CMP-TBB-BBT is as follows: The synthesis of CMP-TBQ-BBT is: According to the molar ratio of TBQ to BBT of 1:(1-3), TBQ is placed in a 35 ml pressure tube, and then 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (BBT), 9 ml of anhydrous DMF, 249 mg of anhydrous potassium carbonate and 4 mg of tetrakis(triphenylphosphine)palladium are added thereto, and then nitrogen is filled into the pressure tube, and the pressure tube is placed at a temperature of 120-200° C. to react for 24-72 hours. After the reaction is completed, the product is cooled, dispersed in DMF, the unreacted raw materials are washed away, and suction is filtered, and then the DMF is washed away with secondary distilled water, suction is filtered, and then anhydrous ethanol is used to fully stir, wash and filter. After the filtration is completed, it is vacuum dried at 100° C. for 10-24 hours. The bright yellow powder obtained after grinding is the target product CMP-TBQ-BBT.

[0020] The synthetic formula of CMP-TBQ-BBT is as follows: As a further optimization of the above two synthesis methods, the nitrogen filling time is not less than 5 minutes, which can ensure that the pressure-resistant tube is filled with nitrogen and thus protect the normal progress of the reaction.

[0021] As a further optimization of the above two synthesis methods, a magnetic particle is added in each synthesis reaction for suspension stirring. Furthermore, the rotation speed is 200r / min. The magnetic particle suspension stirring promotes full contact of the products and promotes the reaction process.

[0022] The above two materials are biphenyl structure conjugated microporous polymers containing thiazole groups. The reactions of the two materials are similar. The process itself has the advantages of simple synthesis steps, convenient operation, low cost, mild reaction conditions, high yield, etc. The finished conjugated microporous polymer contains thiazole groups and introduces nitrogen and sulfur elements, which has broad application prospects in industry and agriculture.

[0023] The present invention provides a conjugated microporous polymer having a bipolyphenyl structure and containing thiazole groups, and the structural formula is: Example 1

[0024] The specific process steps of the preparation process of this embodiment are: Preparation of TBB: 4-Bromoacetophenone (1.1943 g, 6 mmol) was placed in a 100 ml round-bottom flask, 6 ml of anhydrous ethanol was taken using a pipette to dissolve the above solid, and silicon tetrachloride (2.06215 ml, 18 mmol) was slowly added to the solution at room temperature using a pipette to react for 12 hours. After the reaction was completed, 250 mL of saturated ammonium chloride solution was added to the flask, and then rotary evaporated at 60 ° C, followed by extraction with dichloromethane, and the extracted organic matter was rotary evaporated, and the target product was obtained by column chromatography, and then the developing agent was rotary evaporated, and 0.8078 g of 1,3,5-tris (4-bromophenyl) benzene (TBB) was obtained after vacuum drying at 100 ° C (yield 74.8%).

[0025] Preparation of TBQ: 4-(2-bromophenyl)acetophenone (1.644 g, 6 mmol) was placed in a 100 ml round-bottom flask, 6 ml of anhydrous ethanol was taken with a pipette to dissolve the above solid, and silicon tetrachloride (2.06215 ml, 18 mmol) was slowly added to the solution at room temperature with a pipette to react for 12 hours. After the reaction was completed, a small amount of saturated ammonium chloride solution was added to the flask, and then rotary evaporated at 60 ° C, followed by extraction with dichloromethane, and the extracted organic matter was rotary evaporated, and the target product was obtained by column chromatography, and then the developing agent was rotary evaporated, and after vacuum drying at 100 ° C, 0.8817 g of 1,3,5-tris(4-bromo-1,1'-biphenyl-4'-yl)benzene (TBQ) was obtained (yield 57.4%). Example 2

[0026] While keeping other conditions in Example 1 unchanged, the catalyst silicon tetrachloride in the two reactions was changed to borosulfonic acid.

[0027] Put 1.55g of boric acid into a 50ml round-bottom flask, and add 5ml of chlorosulfonic acid dropwise at room temperature. The addition should be completed within 1h, and then nitrogen is filled into the flask. After reacting for 12h, the mixture is washed with ether to remove unreacted chlorosulfonic acid, and then filtered to obtain a gray solid substance, which is pure boric acid.

[0028] Boric acid and 4-bromoacetophenone or 4-(2-bromophenyl)acetophenone are placed in a 35 ml pressure tube, and reacted under magnetic stirring at 100° C. for 12 hours. After the reaction is completed, organic matter is extracted with dichloromethane and water, and then the organic solution is spin-dried, and the target product is separated by column chromatography using a solution of petroleum ether: ethyl acetate 20:1 as a developing solvent. The solution containing the target product is spin-dried to obtain a solid, and finally vacuum dried at 100° C. to obtain TBB (yield is 10.8%) or TBQ (yield is 9.6%).

[0029] The reaction equation for synthesizing TBB from borosulfonic acid and 4-bromoacetophenone is as follows: The reaction equation for the synthesis of TBQ from borosulfonic acid and p-bromoacetophenone is as follows:

[0030] Compared with Example 1, the preparation method of this embodiment has complicated operation procedures and a long reaction cycle. Since the catalyst needs to be prepared before the reaction, the product yield is low, and it involves many experimental tools and high consumption, etc. Therefore, in general, the method of Example 1 has obvious advantages. Example 3

[0031] Under the premise of keeping other conditions in Example 1 unchanged, the operation step of preparing saturated ammonium chloride solution in the process is cancelled. The final yield of TBB is 13.2%; the yield of TBQ is 11.5%. The yield is relatively low. This is because: the preparation of saturated ammonium chloride in the reaction system is to quench the silicon tetrachloride in Example 1, and to remove silicon tetrachloride from the system to prevent the product from further reacting to obtain impurities. The subsequent extraction operation of dichloromethane and water will remove the saturated ammonium chloride solution to ensure the purity of the system material. If the operation of preparing saturated ammonium chloride solution is cancelled, silicon tetrachloride will react with water during extraction to generate silicic acid products, which will affect the extraction of the target organic matter and cause its yield to be low. Therefore, in summary, it is obviously necessary to prepare saturated ammonium chloride solution to quench silicon tetrachloride.

[0032] The product in Example 1 performed best in all aspects. Example 4

[0033] Preparation of CMP-TBB-BBT: TBB (108.62 mg, 0.2 mmol) was placed in a 35 ml pressure tube, and BBT (116.43 mg, 0.3 mmol), 9 ml of anhydrous DMF, anhydrous potassium carbonate (249 mg, 1.8 mmol) and tetrakis(triphenylphosphine)palladium (4 mg, 0.0034 mmol) were added. Then nitrogen was filled into the pressure tube, and the pressure tube was placed at 150°C for 48 hours. After the reaction was completed, the product was cooled, dissolved in DMF, the unreacted raw materials were washed away, and the product was filtered, and the DMF was washed away with secondary distilled water, and then filtered, and then anhydrous ethanol was used to fully stir, wash and filter. After the filtration was completed, it was vacuum dried at 100°C for 24 hours. The bright yellow powder obtained after grinding was 99.4 mg of the target product CMP-TBB-BBT (yield was 97.84%).

[0034] Preparation of CMP-TBQ-BBT: TBQ (154.28 mg, 0.2 mmol) was placed in a 35 ml pressure tube, and BBT (116.43 mg, 0.3 mmol), 9 ml of anhydrous DMF, anhydrous potassium carbonate (249 mg, 1.8 mmol) and tetrakis(triphenylphosphine)palladium (4 mg, 0.0034 mmol) were added. Then nitrogen was filled into the pressure tube, and the pressure tube was placed at 150°C for 48 hours. After the reaction was completed, the product was cooled, dissolved in DMF, the unreacted raw materials were washed away, and the product was filtered, and the DMF was washed away with secondary distilled water, filtered, and then anhydrous ethanol was used to stir, wash and filter. After the filtration was completed, it was vacuum dried at 100°C for 24 hours. The bright yellow powder obtained after grinding was 110.6 mg of the target product CMP-TBQ-BBT (yield was 75.96%). Example 5

[0035] Under the premise of keeping other conditions in Example 4 unchanged, the reaction temperature of the two was changed to 120°C. It was found that within the prescribed 48h, the reaction was incomplete, which was not conducive to the efficient completion of the reaction, and the product yield was relatively low (the yield of CMP-TBB-BBT was 8.2%; the yield of CMP-TBQ-BBT was 6.3%). When the reaction temperature was changed to 200°C, the temperature increase can accelerate the reaction rate and improve the experimental progress, but at 200°C, it exceeds the boiling point of anhydrous DMF, affecting the reaction process, and the product yield also decreased (the yield of CMP-TBB-BBT was 16.4%; the yield of CMP-TBQ-BBT was 5.421%), and the decomposition products were harmful to both the human body and the environment. Therefore, in summary, the temperature described in Example 4 is the optimal temperature. Example 6

[0036] Under the premise of keeping other conditions in Example 4 unchanged, when the anhydrous potassium carbonate content of the two is changed to 1mmol, that is, (138.33mg), the alkalinity of the reaction system is not strong, resulting in the intermediate product in the reaction process not being eliminated in time, affecting the purity of the system and the yield of the product (wherein the yield of CMP-TBB-BBT is 63.0%; the yield of CMP-TBQ-BBT is 40.1%). When the anhydrous potassium carbonate content is changed to 3mmol, that is, (415mg), the alkalinity of the reaction system is strong enough to ensure that the intermediate product in the system is eliminated, and will eventually be removed by distilled water, and the yield is equivalent to that of Example 4 (wherein the yield of CMP-TBB-BBT is 96.42%; the yield of CMP-TBQ-BBT is 76.81%). However, the effect achieved by anhydrous potassium carbonate in Example 4 is consistent with the above. In order to save resources and reduce experimental costs, the content of anhydrous potassium carbonate in Example 4 is the optimal condition. Example 7

[0037] Under the premise of keeping other conditions in Example 4 unchanged, the reaction time was increased to 72h, and it was found that the yields of CMP-TBB-BBT and CMP-TBQ-BBT were basically unchanged (the yield of CMP-TBB-BBT was 96.84%; the yield of CMP-TBQ-BBT was 74.39%), which was consistent with the phenomenon of the reaction time of 48h. The reaction time was 24h, and the product yield was not high (the yield of CMP-TBB-BBT was 56.31%; the yield of CMP-TBQ-BBT was 41.25%). In order to improve the experimental progress and save time, a reaction time of 48h is the most appropriate. Analysis and characterization of finished biphenyl structured conjugated microporous polymers containing thiazole groups:

[0038] The performance of TBB and TBQ synthesized in Example 1 of the present invention, and CMP-TBB-BBT and CMP-TBQ-BBT synthesized in Example 4 were analyzed.

[0039] FT-IR analysis: Figure 8 FT-IR graphs of the raw materials TBB and BBT used in the present invention and CMP-TBB-BBT synthesized therefrom. The top line is the infrared spectrum line of TBB, 3448 cm -1 The peak at 813 cm is attributed to the stretching vibration of the CH bond on the benzene ring. -1 and 505cm -1 The peaks at 3620cm are caused by the stretching vibration and bending vibration of the C-Br bond. The bottom line is the infrared spectrum line of BBT, 3620cm -1 and 3545cm -1 The peak at 2982 cm is attributed to the stretching vibration of the CH bond.-1 and 2932cm -1 The peak at 1618 cm is caused by the stretching vibration of the CH bond in -CH3. -1 The peak at is caused by the skeleton vibration of the thiazole group; the middle line is the infrared spectrum of CMP-TBB-BBT. It can be seen from the line that the characteristic peak of the thiazole group is reflected in the spectrum of CMP-TBB-BBT, proving that the thiazole group is successfully grafted. The shadow shows that the C-Br bond and the boryl ester alkane undergo coupling condensation, and the corresponding top line is 813cm -1 and 505cm -1 , 3620cm on the bottom line -1 and 3545cm -1 、2982cm -1 and 2932cm -1 The peak at disappears on the middle line, proving the successful synthesis of CMP-TBB-BBT.

[0040] Fig.16 FT-IR graphs of the raw materials TBQ and BBT used in the present invention and CMP-TBQ-BBT synthesized therefrom. The top line is the infrared spectrum line of TBQ, 3448 cm -1 The peak at 808 cm is attributed to the stretching vibration of the CH bond on the benzene ring. -1 and 494cm -1 The peaks at 3620cm are caused by the stretching vibration and bending vibration of the C-Br bond. The bottom line is the infrared spectrum line of BBT, 3620cm -1 and 3545cm -1 The peak at 2922 cm is attributed to the stretching vibration of the CH bond. -1 The peak at 1481 cm is caused by the stretching vibration of the CH bond in -CH3. -1 The peak at 1618 cm is caused by the stretching vibration of C=C on the aromatic ring. -1 The peak at 808 cm is caused by the skeleton vibration of the thiazole group. The middle line is the infrared spectrum of CMP-TBQ-BBT. It can be seen from the line that the characteristic peak of TBQ is reflected in the spectrum of CMP-TBQ-BBT. The shadow shows that the C-Br bond and the boryl ester are coupled and condensed. The corresponding top line is 808 cm -1 and 494cm -1 , 3620cm on the bottom line -1 and 3545cm -1 , 2922cm -1 The peak at 40° disappears on the middle line, proving the successful synthesis of CMP-TBQ-BBT.

[0041] Scanning electron microscopy analysis: Figure 6 and Figure 7 This is a scanning electron microscope image of the CMP-TBB-BBT material synthesized by the present invention; Fig.14 and Fig.15 This is a scanning electron microscope image of the CMP-TBQ-BBT material synthesized by the present invention. Figure 6 , Figure 7 , Fig.14 and Fig.15 It can be clearly seen that the material synthesized by the coupling method in the preparation process of the present invention has the characteristics of being fluffy and porous, and performs well in adsorption. The microscopic morphology of the synthesized material is observed by means of a scanning electron microscope. It can be seen from the scanning electron microscope photos that the two product materials are fluffy, the pores are uniform, the particle surface is relatively rough, and the structure size is different. The particle size of the material CMP-TBB-BBT is about 300nm to 600nm, and the particle size of the material CMP-TBQ-BBT is about 100nm to 300nm. No strip, lamellar or block morphology was observed in the system, and all of them showed spherical shapes of different morphologies, and there was a certain degree of agglomeration.

[0042] It should be noted that the above-described embodiments should be understood as illustrative rather than limiting the scope of protection of the present invention, and the scope of protection of the present invention shall be subject to the claims. For those skilled in the art, some non-essential improvements and adjustments made to the present invention still fall within the scope of protection of the present invention without departing from the essence and scope of the present invention.

Claims

1. A conjugated microporous polymer having a biphenyl structure and containing thiazole groups, characterized in that: The structural formula of the conjugated microporous polymer is:

2. The method for preparing the biphenyl structure conjugated microporous polymer containing thiazole groups according to claim 1, characterized in that: The following steps are involved: Step 1, weighing silicon tetrachloride and 4-bromoacetophenone or 4-(2-bromophenyl)acetophenone respectively in a molar ratio of (1-3):1, then dissolving the weighed 4-bromoacetophenone or 4-(2-bromophenyl)acetophenone in anhydrous ethanol, and after being completely dissolved, adding the weighed silicon tetrachloride dropwise thereto, and carrying out a mixing reaction under continuous stirring for 10-14 hours, then adding a saturated ammonium chloride solution to the obtained mixture, mixing it thoroughly, and then subjecting it to rotary evaporation at 40-60°C, and then first extracting the remaining product after rotary evaporation with dichloromethane, and then separating the primary product with a developing agent by column chromatography, and then removing the developing agent in the primary product by rotary evaporation, and vacuum drying at 95-105°C to obtain 1,3,5-tris(4-bromophenyl)benzene or 1,3,5-tris(4-bromo-1,1'-biphenyl-4'-yl)benzene for standby use; Step 2: Weigh 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole and 1,3,5-tri(4-bromophenyl)benzene or 1,3,5-tri(4-bromo-1,1'-biphenyl-4'-yl)benzene prepared in step 1 in a molar ratio of (1-3):1, and then weigh the weighed 1,3,5-tri(4-bromophenyl)benzene or 1,3,5-tri(4-bromo- 1,1'-biphenyl-4'-yl)benzene is placed in a pressure vessel, and then 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-2,1,3-benzothiadiazole and anhydrous N,N'-dimethylformamide, anhydrous potassium carbonate and tetrakis(triphenylphosphine)palladium are added thereto, and the pressure tube is placed in a temperature environment of 120-200°C for reaction for 24-72h under the conditions of inert gas protection and continuous stirring; Step 3: After the reaction is completed and the product is cooled, the obtained reaction product is washed with N,N'-dimethylformamide, filtered, and then washed with distilled water to remove N,N'-dimethylformamide. After filtering again, it is washed with ethanol, then filtered, and then placed in a vacuum drying environment at a temperature of 95-105°C for 10-24h. After grinding, a bright yellow powder target product CMP-TBB-BBT or CMP-TBQ-BBT is obtained.

3. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 1, the molar ratio between the 4-bromoacetophenone or 4-(2-bromophenyl)acetophenone and silicon tetrachloride is 1:

3.

4. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 1, the developing solvent used for column chromatography separation is a mixed solvent of dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether in the mixed solvent is 1:

1.

5. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 1, the addition ratio between the 4-bromoacetophenone or 4-(2-bromophenyl)acetophenone and anhydrous ethanol is 0.9-1.2 mol / L.

6. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 1, the mixing reaction time of 4-bromoacetophenone or 4-(2-bromophenyl)acetophenone and silicon tetrachloride is 12 hours.

7. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 2, the molar ratio of 1,3,5-tri(4-bromophenyl)benzene or 1,3,5-tri(4-bromo-1,1'-biphenyl-4'-yl)benzene to 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-2,1,3-benzothiadiazole is 2:

3.

8. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 2, the mass ratio of anhydrous N,N'-dimethylformamide, anhydrous potassium carbonate and tetrakis(triphenylphosphine)palladium added is 9:24:

4.

9. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 2, the inert gas is nitrogen, and the pressure container is filled with nitrogen for no less than 5 minutes, the reaction temperature is 150° C., and the reaction time is 48 hours.

10. The method for preparing the bipolyphenyl structure conjugated microporous polymer containing thiazole groups according to claim 2, characterized in that: In step 1 and step 2, the stirring speed is 200 r / min.

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