Alkynyl-containing conjugated microporous polymers in a helical structure, and methods of making and using the same

Abstract

The application discloses acetylenic group-containing conjugated microporous polymers in a spiral structure and a preparation method thereof. A preparation process takes TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene as raw materials, takes tetra(triphenylphosphine palladium) and CuI as a catalyst, and takes toluene as a solvent. Through structural optimization and modular design of target CMPs, two kinds of conjugated microporous polymers CMP-1 and CMP-2 are prepared based on a Sonogashira coupling reaction mechanism by a solvothermal method. The conjugated microporous polymers have the characteristics of novel raw material structure, simple synthesis process, low cost, mild reaction condition and high yield. The synthesized CMP-1 and CMP-2 have an extended pi electron system, so that the CMP-1 and CMP-2 exhibit good electronic transmission performance. The materials have potential application values in photoelectric devices, such as organic light-emitting diodes, solar cells and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of synthesis of conjugated microporous polymers (CMPs), in particular to two kinds of conjugated microporous polymers containing alkynyl with spiral structure and preparation method and application thereof. BACKGROUND

[0002] Conjugated microporous polymers (CMPs) are a kind of organic porous polymers, which have both π conjugated skeleton and a large number of micropores in the molecular structure compared with conventional conjugated polymers or porous materials. As a new material platform, CMPs integrate the advantages of conjugated skeleton and microporous, have large specific surface area, excellent chemical stability and good thermal stability, and show great potential in solving energy and environmental problems. CMPs have shown great application prospects in many fields such as gas adsorption, heterogeneous catalysis, luminescent materials, chemical sensors, electrical energy storage and biological hybrids.

[0003] At present, a variety of new methods for designing and synthesizing CMPs structural units have been developed in the prior art, which are used to prepare a variety of CMPs with different structures and specific properties, effectively promoting the rapid development of this field. In the synthesis process of CMPs, a trifurcated center molecule is usually used as the core, a linear group molecule is used as the linker, and the core molecule and the linker molecule are covalently connected by π conjugated bond through synthesis reaction, so as to construct a conjugated skeleton.

[0004] The defects of this traditional method are as follows: 1. The structure of raw materials is single, which leads to the limitation of the structure of synthesized CMPs, the use and the material performance; 2. There are many by-products in the reaction, which leads to low product purity, poor product quality and many post-processing steps; 3. The reaction conditions are relatively harsh, and the production safety is poor.

[0005] Therefore, how to design the structure of CMPs so as to have the advantages of novel structure, simple process steps, mild reaction conditions, high product purity and the like is of great significance for improving the development and application of conjugated microporous polymer materials. SUMMARY

[0006] The technical purpose of the present application is to provide two kinds of conjugated microporous polymers containing alkynyl with spiral structure and preparation method thereof. The reaction raw materials with high energy matching degree and good mutual selectivity are designed, and the Sonogashira coupling reaction is used to construct functional conjugated microporous polymers with novel structure. The method has the advantages of simple process steps, mild reaction conditions, high efficiency, good selectivity, novel structure of finished CMPs, high yield and good purity, and has potential application value in the field of optoelectronic devices.

[0007] To achieve the above object, the technical scheme adopted by the present application is as follows: a conjugated microporous polymer containing alkyne groups in a spiral structure, the structural formula of the conjugated microporous polymer is:

[0008]

[0009] A preparation method of a conjugated microporous polymer containing alkyne groups in a spiral structure, comprising the following steps:

[0010] TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene are taken as reaction raw materials, CuI and tetrakis(triphenylphosphine)palladium are taken as reaction aids, and are dissolved in a pressure-resistant tube containing triethylamine and anhydrous toluene, then the obtained reaction system is placed in an oil bath pot at 60-90 DEG C for stirring reaction for 12-24 h, after the reaction is completed, static aging, suction filtration and washing are sequentially performed, then Soxhlet extraction is performed with methanol for 20-30 h, and after vacuum freeze-drying and grinding treatment, loose dark brown powder target product CMP-1 and dark brown powder target product CMP-2 are obtained.

[0011] Preferably, the molar ratio of TNP-3Br to 1,4-diethynylbenzene in the reaction raw materials is 2:(2-4), and the molar ratio of TNP-3Br to 1,4-diethynylbenzene is 2:(1-3).

[0012] Preferably, the molar ratio of TNP-3Br to 1,4-diethynylbenzene in the reaction raw materials is 2:3, and the molar ratio of TNP-3Br to 1,4-diethynylbenzene is 1:1.

[0013] Preferably, the reaction temperature of the reaction system is 80 DEG C, and the reaction time is 12 h.

[0014] Preferably, the reaction system needs to be subjected to freeze-thaw cycle degassing treatment before stirring reaction.

[0015] Preferably, the static aging time is 10-15 h.

[0016] Preferably, the washing of the reaction product is sequentially performed with DMF, water and acetone, and each washing agent is repeated for 1-3 times, the Soxhlet extraction time is 24 h, and the vacuum freeze-drying time is 12 h.

[0017] Preferably, the preparation method of the anhydrous toluene is as follows: sodium wire is added to toluene as a drying agent, benzophenone is used as an indicator, after the color of the toluene solution changes to purple, the toluene solution is subjected to distillation treatment by atmospheric distillation, and the fraction at 110 DEG C is collected, thereby obtaining anhydrous toluene.

[0018] Application of acetylenic group-containing conjugated microporous polymers with helical structure in chiral recognition and separation, optical sensor, organic field effect transistor and organic solar cell.

[0019] Advantages:

[0020] 1. The preparation process of the application uses TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene as raw materials, tetrakis(triphenylphosphine palladium) and CuI as catalysts, and toluene as solvent, and through structure optimization and modular design of target CMPs, two conjugated microporous polymers CMP-1 and CMP-2 are prepared by solvothermal method based on Sonogashira coupling reaction mechanism. The application has the characteristics of novel structure of raw materials, simple synthesis process, low cost, mild reaction conditions and high yield; the synthesized CMP-1 and CMP-2 have extended pi electron system, which exhibits good electronic transmission performance. These materials have potential application value in optoelectronic devices such as organic light emitting diodes, solar cells and the like.

[0021] 2. The synthesized CMP-1 and CMP-2 of the application are in helical structure, which can make the conjugated system of the polymer produce special optical activity such as circular dichroism and optical rotation, and can be used in the fields of chiral recognition and separation, optical sensor and the like; the conjugated system of the polymer provides a channel for electron delocalization, and the helical structure increases the complexity and diversity of the electron transmission path, so that the electron can be transmitted more efficiently, and therefore the application has potential application value in organic electronic devices such as organic field effect transistor, organic solar cell and the like.

[0022] 3. The synthesis process of the application selects TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene for matching in raw material selection, and when TNP-3Br in the raw material reacts with ethynyl-containing benzene, the electron energy in the HOMO orbital of the ethynyl-containing benzene is relatively high and relatively active, the carbon-bromine bond connected with the bromine atom in TNP-3Br has a certain polarity, resulting in that the LUMO orbital energy of the carbon atom is relatively low, the matching degree of the orbital energy is good, so that the reaction can be smoothly carried out under relatively mild conditions, the activation energy of the reaction is reduced, the efficiency and selectivity of the reaction are improved, and therefore the yield and purity of the finished product CMPs are improved.

[0023] 4. The solvothermal reaction process of the application is carried out in a pressure-resistant pipe, compared with a conventional reaction container, the reaction which originally needs higher temperature under normal pressure can be carried out under relatively low temperature and high pressure, which is beneficial to improve the reaction selectivity and yield, and can reduce the occurrence of side reactions, and the pressure-resistant pipe is convenient to operate and has simple process.

[0024] 5、The synthetic process of the present application selects anhydrous toluene as a reaction reagent, and the preparation method of the anhydrous toluene is as follows: toluene is added with sodium wire as a drying agent, and benzophenone is used as an indicator; when the color turns blue, it indicates that there is no oxygen; when the color turns purple, it indicates that there is no water; when the color becomes deeper, it is distilled under normal pressure, and the fraction collected at 110 DEG C is obtained. The anhydrous toluene greatly improves the anhydrous environment of the experiment, and further reduces the occurrence of side reactions.

[0025] 6、The synthetic process of the present application adopts a vacuum freeze drying method for dehydrating the product, and the advantage is that, compared with the traditional air drying, the water can be directly sublimated from solid to gas (i.e. the freeze drying process) or quickly removed through liquid evaporation under vacuum conditions, so that the drying cycle is greatly shortened. Since the drying process is carried out at low temperature, the color, odor and micropore structure of the raw material can be well preserved, which is particularly important for heat-sensitive substances, so that the yield, purity and specific area of the product are greatly improved. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The infrared spectrum of the CMPs material synthesized in the embodiment 1 of the present application;

[0027] Figure 2 The scanning electron microscope graph of the CMP-1 material synthesized in the embodiment 1 of the present application;

[0028] Figure 3 The scanning electron microscope graph of the CMP-2 material synthesized in the embodiment 1 of the present application;

[0029] Figure 4 The nitrogen adsorption and desorption graph of the CMP-1 material synthesized in the embodiment 1 of the present application;

[0030] Figure 5 The pore size graph of the CMP-1 material synthesized in the embodiment 1 of the present application;

[0031] Figure 6 The nitrogen adsorption and desorption graph of the CMP-2 material synthesized in the embodiment 1 of the present application. DETAILED DESCRIPTION

[0032] The present application will be further described in detail in combination with the drawings and specific embodiments:

[0033] The present application provides two kinds of conjugated microporous polymers containing alkynyl groups with a spiral structure and a synthesis method thereof, and the synthesis principles of the two kinds of conjugated microporous polymers containing alkynyl groups with a spiral structure are the same, and the synthesis of CMP-1 is as follows:

[0034] According to the molar ratio of 2:(2-4), the reaction raw material TNP-3Br and 1,4-diethynylbenzene are taken, CuI and tetrakis(triphenylphosphine)palladium are taken as catalysts, and the above-mentioned are dissolved in a pressure tube containing triethylamine and toluene; the obtained mixed solution is subjected to freeze-thaw cycle degassing treatment, and then is placed in an oil bath at 60-90 DEG C for stirring reaction for 12-24h; after the reaction is completed, standing and aging for 10-15h, suction filtration, the product is washed with DMF, water and acetone for several times, after washing, Soxhlet extraction is carried out with methanol for 20-30h, and finally vacuum freeze-drying for 12h, and after grinding, a dark brown powder, i.e. the target product CMP-1, is obtained.

[0035] The reaction synthesis formula is as follows:

[0036]

[0037] The synthesis of CMP-2 is as follows:

[0038] According to the molar ratio of 2:(1-3), the reaction raw material TNP-3Br and 1,3,5-triethynylbenzene are taken, CuI and tetrakis(triphenylphosphine)palladium are taken as catalysts, and the above-mentioned are dissolved in a pressure tube containing triethylamine and toluene; the obtained mixed solution is subjected to freeze-thaw cycle degassing treatment, and then is placed in an oil bath at 60-90 DEG C for stirring reaction for 12-24h; after the reaction is completed, standing and aging for 10-15h, suction filtration, the product is washed with DMF, water and acetone for several times, after washing, Soxhlet extraction is carried out with methanol for 20-30h, and finally vacuum freeze-drying for 12h, and after grinding, a dark brown powder, i.e. the target product CMP-2, is obtained.

[0039] The reaction synthesis formula is as follows:

[0040]

[0041] The structure characteristics and features of the synthesized conjugated microporous polymers CMP-1 and CMP-2 are as follows:

[0042] The present application takes TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene as raw materials, tetrakis(triphenylphosphine)palladium and CuI as catalysts, and toluene as solvent, and two kinds of conjugated microporous polymers CMP-1 and CMP-2 are prepared by using solvothermal method. The present application has the characteristics of novel raw material structure, simple synthesis process, low cost, mild reaction condition and high yield; the synthesized CMP-1 and CMP-2 have extended pi electron system, so that they exhibit good electronic transmission performance. These materials have potential application value in photoelectric devices, such as organic light emitting diode, solar cell, etc., and have good application prospect.

[0043] Example 1

[0044] The preparation process of the present embodiment includes the following specific preparation steps:

[0045] TNP-3Br (382.68 mg, 0.6 mmol) and 1,4-diethynylbenzene (113.535 mg, 0.9 mmol) or 1,3,5-triethynylbenzene (93.6 mg, 0.6 mmol), tetrakis(triphenylphosphine)palladium (50 mg) and CuI (15 mg) were dissolved in a pressure tube containing triethylamine (2 ml) and anhydrous toluene (2 ml), degassed by three freeze-thaw cycles, the mixture was stirred in an 80°C oil bath for 12 h, the reaction was stopped and naturally cooled to room temperature, and then aged for 12 h before being filtered under suction. The product was first washed with DMF to remove unreacted TNP-3Br, 1,4-diethynylbenzene, tetrakis(triphenylphosphine)palladium and CuI, then washed with distilled water twice to remove the residual DMF molecules on the surface and in the pores of the sample, and finally washed with acetone to remove the oligomers and impurities. After the washing was completed, the sample was Soxhlet extracted with methanol for 24 h, vacuum freeze-dried for 12 h, and then ground to obtain dark brown powder CMP-1 and dark brown powder CMP-2.

[0046] It was determined that the product CMP-1 and CMP-2 prepared in the present embodiment had a yield of 73.2% for CMP-1, a specific surface area of 270.83 m 2 / g, a pore size of 1.59 nm, and a Langmuir specific surface area of 462.23 m 2 / g; and a yield of 68.3% for CMP-2 (the yield was reduced because the 1,3,5-triethynylbenzene molecules were smaller than the TNP-3Br and were more difficult to combine), a specific surface area of 261.46 m 2 / g, a pore size of 1.59 nm, and a Langmuir specific surface area of 440.37 m 2 / g.

[0047] Example 2

[0048] Increasing the proportion of the alkyne group ligand (the molar ratio of TNP-3Br to 1,4-diethynylbenzene in the raw materials was 2:3.5, and the molar ratio of TNP-3Br to 1,3,5-triethynylbenzene was 2:2.5) while keeping other conditions unchanged in Example 1 can slightly increase the specific surface area of the product, because the bromine group ligand can fully react with the excess alkyne group ligand, and the unreacted alkyne group ligand is relatively easy to separate from the reaction product, making the polymer irregular. Therefore, the molar ratio of TNP-3Br to 1,4-diethynylbenzene (1,3,5-triethynylbenzene) can be appropriately adjusted, and preferably the molar ratio of TNP-3Br to 1,4-diethynylbenzene in the raw materials is 2:3, and the molar ratio of TNP-3Br to 1,4-diethynylbenzene is 2:2.

[0049] Example 3

[0050] In Example 1, other conditions remain unchanged, while the amount of solvent anhydrous toluene is reduced to 1 ml, the concentration of base is enhanced, which makes the activity of the catalyst decreases, and is not conducive to the reaction. Therefore, the amount of solvent toluene should be maintained at 2-2.5 ml.

[0051] Example 4

[0052] In Example 1, other conditions remain unchanged, while the reaction solvent anhydrous toluene is replaced by anhydrous N,N'-dimethylformamide (DMF), it is found that the color of the reactants presents black. It is determined that in addition to a small amount of product, there will be more black impurities. Analysis shows that: DMF has strong hygroscopicity, easy to absorb moisture in the air, destroy the anhydrous environment of the reaction, therefore, the reaction should be carried out in anhydrous toluene solvent.

[0053] Example 5

[0054] In Example 1, other conditions remain unchanged, while the triethylamine is replaced by anhydrous potassium carbonate, it is found that the reaction is basically not carried out. It is found that anhydrous potassium carbonate is basically insoluble in toluene, and the reaction is difficult to react without the participation of base, even not to react. Generally speaking, organic base is conducive to the polymerization reaction, therefore, triethylamine is relatively more suitable as the base of the reaction.

[0055] Example 6

[0056] In Example 1, other conditions remain unchanged, while the reaction temperature is increased to 100°C, it is found that the reaction is more quickly completed, but with the further progress of the reaction, the product will present black brown, and the precipitate is very little. It is determined that the yield is greatly reduced, because at higher temperature, the molecular thermal motion is increased, thus increasing the collision frequency and energy transfer between the reactions, making the structure of the product generated is destroyed. Therefore, the reaction temperature should be controlled at 60-90°C.

[0057] Example 7

[0058] In Example 1, other conditions remain unchanged, while the reaction time is increased to 48h, it is found that the phenomenon is consistent with Example 6, the reaction product will present black brown and the precipitate is less. It is determined that the specific surface area is smaller, because the reaction 12h has a good microporous structure, with the increase of reaction time, the microporous structure formed will be irreversible deformation, changing the morphology of the molecules. Therefore, the reaction time should be controlled at 12-24h.

[0059] Example 8

[0060] The reaction was carried out by replacing the pressure tube with a reaction kettle while keeping other conditions in Example 1 unchanged. It was found that the experimental operation was extremely inconvenient because the sample amount required in the experiment was small, the pressure tube was easier to use for experimental operation, and the pressure tube had a large surface area to volume ratio, which helped to improve the heat exchange efficiency, making the temperature control more accurate and rapid.

[0061] Example 9

[0062] In Example 1, the freeze-drying was replaced by heating drying while keeping other conditions unchanged. It was found that the morphology of the product partially collapsed under the electron microscope because the high temperature destroyed the microstructure of the product. Freeze-drying process does not cause the destruction of molecules, and can better maintain the original morphology and microstructure of the material. Freeze-drying can remove most of the bound water in the material, and the residual moisture in the final product is usually less than 5%, which is particularly advantageous for products that need to be stored for a long time.

[0063] In the above examples, brownish powder began to adhere to the wall of the reaction container after about 3 hours of reaction. To avoid slow reaction, the temperature can be appropriately increased to 80°C.

[0064] Analysis and characterization of the finished product of the acetylenic group-containing conjugated microporous polymer material with a spiral structure:

[0065] Performance analysis of CMP-1 and CMP-2 synthesized in Example 1 of the present application.

[0066] FT-IR analysis: Figure 1 FT-IR graphs of the raw materials containing bromine intermediates and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene, and CMP-1 and CMP-2 synthesized therefrom used in the present application. Figure 1 The lines in the figure from top to bottom include three solid lines and two dashed lines, i.e. from top to bottom, they are the upper first solid line, the upper first dashed line, the middle second solid line, the lower second dashed line and the lower third solid line. Among them, the upper first solid line is the infrared spectrum line of 1,4-diethynylbenzene, the peaks at 3250 cm -1 , 3000 cm -1 and 2100 cm -1 are attributed to the stretching vibration of C-H bond, and the peaks at 550 cm -1 and 498 cm -1 are attributed to the bending vibration of C≡C bond; the middle second solid line is the infrared spectrum line of the bromine-containing intermediate, the two groups of peaks at 943 cm -1 and 533 cm -1 are caused by the stretching vibration and bending vibration of C-Br; the upper first dashed line is the infrared spectrum line of CMP-1, from Figure 1The strong bands indicated by the middle shaded portion can be deduced that the characteristic peaks of the starting material 1,4-diethynylbenzene and the bromine-containing intermediate are all present in the product CMP-1, which can prove the integrity of the product. When the Br on the C-Br bond couples off with the alkyne group, the peaks at 3250 cm -1 , 943 cm -1 and 533 cm -1 on the upper first solid line disappear on the upper first dashed line, which proves the successful synthesis of CMP-1.

[0067] Figure 1 The middle lower third solid line is the infrared spectrum line of 1,3,5-triethynylbenzene, the peak at 3277 cm -1 is attributed to the stretching vibration of C-H bond, the peaks at 672 cm -1 and 613 cm -1 are attributed to the bending vibration of C≡C bond; the middle second solid line is the infrared spectrum line of the bromine-containing intermediate, the two groups of peaks at 943 cm -1 and 533 cm -1 are caused by the stretching vibration and bending vibration of C-Br; the lower second dashed line is the infrared spectrum line of CMP-2, from Figure 1 the strong bands indicated by the middle shaded portion can be deduced that the characteristic peaks of the starting material 1,3,5-triethynylbenzene and the bromine-containing intermediate are all present in the product CMP-2, which can prove the integrity of the product. When the Br on the C-Br bond couples off with the alkyne group, the peaks at 3277 cm -1 , 943 cm -1 and 533 cm -1 on the upper first solid line disappear on the upper first dashed line, which proves the successful synthesis of CMP-2.

[0068] Scanning electron microscope analysis:

[0069] Scanning electron microscope (SEM) is a means for observing the morphology and composition of the ultrastructure of the surface of a solid, which is between a transmission electron microscope and an optical microscope. It uses a very narrow high-energy electron beam to scan the sample, and various physical information is excited through the interaction between the light beam and the matter. When the scanning electron beam interacts with the sample, various signals are generated, including secondary electrons, absorbed electrons, Auger electrons, backscattered electrons and X-rays, etc., among which the secondary electrons are the most important. The scanning electron microscope generally uses an electron beam to scan the surface of the sample, and then collects the generated secondary electrons with a special detector to form an electric signal which is sent to the imaging tube, and finally the object morphology is displayed on the fluorescent screen. These information is collected, amplified and re-imaged to achieve the purpose of characterizing the micro-morphology of the material.

[0070] Figure 2 , Figure 3 The images shown are scanning electron microscope (SEM) images of the two materials synthesized in Example 1 of this invention, which show the microstructure of the synthesized conjugate microporous materials. Figure 2 , Figure 3 Scanning electron microscope images show that the particles of materials CMP-1 and CMP-2 are of different sizes, with relatively rough surfaces, uniform pores, and a particle size of about 1 to 3 micrometers. They are spherical and do not have ribbon-like, fibrous, or rod-like shapes, and exhibit a certain degree of agglomeration.

[0071] Nitrogen adsorption-desorption curve analysis:

[0072] Figure 4 Nitrogen gas at 77K CMP-1 (pore size) Adsorption-desorption isotherms, hollow circles are desorption isotherms, and solid circles are adsorption isotherms; Figure 5 The pore size distribution of CMP-1 was calculated using the DFT method with the nitrogen adsorption-desorption isotherm as the standard. During the study, after determining the structure of the organic porous material, its pore size characteristics and specific surface area, among other properties, needed to be characterized. The procedure was as follows: First, the sample powder was thoroughly ground. To remove guest solvent molecules from the framework pores, it was vacuum-dried at 100℃ for 12 hours before testing. Then, nitrogen adsorption-desorption tests were performed on CMP-1 at 77K. The results showed that the product exhibited a typical type I gas adsorption curve, indicating the presence of a microporous structure in CMP-1. Analysis Figure 4 It was found that the adsorption curve rose slowly, while the desorption curve lagged behind. References indicate that this phenomenon is due to the unique swelling properties of the organic framework. The BET model specific surface area of ​​CMP-1 is 270.83 m². 2 ·g -1 The specific surface area of ​​Langmuir is 462.23 m². 2 ·g -1 According to the density enthalpy transformation (DFT) model, the microporous material has a uniform pore size distribution.

[0073] Figure 6 Nitrogen gas at 77K for CMP-2 (pore size) ) adsorption and desorption isotherms, hollow circles are desorption isotherms, and solid circles are adsorption isotherms. In the research process, after the structure of the organic porous material is determined, the pore size characteristics and specific surface area and other properties need to be characterized. The operation is as follows: first, the sample powder is ground thoroughly, in order to remove the guest solvent molecules in the framework pores, it needs to be placed in a 100°C environment for vacuum drying for 12 hours before testing, then nitrogen adsorption-desorption test experiment is carried out on CMP-2 at 77K, it is found that the product has a typical type I gas adsorption curve, which shows that there is a microporous structure in CMP-1. Figure 6 It is found that the adsorption curve rises slowly, and the desorption curve lags behind, and according to the reference, this phenomenon is caused by the unique swelling characteristics of the organic framework. The BET model specific surface area of CMP-2 is 261.46m 2 ·g -1 , the Langmuir specific surface area is 440.37m 2 ·g -1 , according to the density functional theory (DFT) model analysis, the pore size distribution of the microporous material is uniform.

[0074] It should be noted that the above-mentioned embodiments should be understood as illustrative, rather than limiting the protection scope of the present application, and the protection scope of the present application is subject to the claims. For those skilled in the art, some non-essential improvements and adjustments of the present application without departing from the spirit and scope of the present application still belong to the protection scope of the present application.

Claims

1. A method for preparing a conjugated microporous polymer containing alkynyl groups in a helical structure, characterized by, The method comprises the following steps: TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene are taken as reaction raw materials, CuI and tetrakis(triphenylphosphine)palladium are taken as reaction aids, and are dissolved in a pressure-resistant tube containing triethylamine and anhydrous toluene, then the obtained reaction system is placed in an oil bath pot at 60-90 DEG C for stirring reaction for 12-24 h, after the reaction is completed, static aging, filtration and washing are sequentially performed, then Soxhlet extraction is performed with methanol for 20-30 h, and after vacuum freeze-drying and grinding treatment, loose dark brown powder target product CMP-1 and dark brown powder target product CMP-2 are obtained. The molar ratio of TNP-3Br to 1,4-diethynylbenzene is 2: (2-4), and the molar ratio of TNP-3Br to 1,3,5-triethynylbenzene is 2: (1-3). The structural formula of the TNP-3Br is: 。 2. The method of claim 1, wherein the preparation of the alkyne-containing conjugated microporous polymer in a helical structure is characterized by: The molar ratio of TNP-3Br to 1,4-diethynylbenzene is 2:3, and the molar ratio of TNP-3Br to 1,3,5-triethynylbenzene is 1:

1.

3. The method for preparing the helical-structured alkyne-containing conjugated microporous polymer according to claim 1, characterized in that: The reaction temperature of the reaction system is 80 DEG C, and the reaction time is 12 h.

4. The method of claim 1, wherein the preparation of the acetylene group-containing conjugated microporous polymer in a spiral structure is characterized by: The reaction system needs to be subjected to freeze-thaw cycle degassing treatment before stirring reaction.

5. The method for preparing the helical-structured alkyne-containing conjugated microporous polymer according to claim 1, characterized in that: The static aging time is 10-15 h.

6. The method for preparing the helical-structured alkyne-containing conjugated microporous polymer according to claim 1, characterized in that: The reaction product is washed with DMF, water and acetone in sequence, and each washing is repeated for 1-3 times, the Soxhlet extraction time is 24 h, and the vacuum freeze-drying time is 12 h.

7. The method for preparing the helical-structured alkyne-containing conjugated microporous polymer according to claim 1, characterized in that, The preparation method of the anhydrous toluene is as follows: sodium filaments are added into toluene as a drying agent, benzophenone is used as an indicator, after the color of the toluene solution changes to purple, the toluene solution is subjected to distillation treatment by using normal pressure distillation, and the fraction at 110 DEG C is collected, and the anhydrous toluene is obtained.

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