Alkynyl-containing conjugated microporous polymer with helical structure as well as preparation method and application of alkynyl-containing conjugated microporous polymer

Abstract

According to the preparation process, TNP-3Br and 1, 4-diacetylene benzene or 1, 3, 5-triacetylene benzene are used as raw materials, tetrakis (triphenylphosphine palladium) and CuI are used as catalysts, toluene is used as a solvent, through structural optimization and modular design of target CMPs, a solvothermal method is adopted based on a Sonogashira coupling reaction mechanism, and the alkynyl-containing conjugated microporous polymer with a helical structure is prepared. The two conjugated microporous polymers CMP-1 and CMP-2 are prepared, and the conjugated microporous polymers have the characteristics of novel raw material structure, simple synthesis process, low cost, mild reaction conditions, high yield and the like; the synthesized CMP-1 and CMP-2 have extended pi electronic systems, so that the CMP-1 and CMP-2 show good electronic conduction performance. The materials have potential application value in photoelectric equipment, such as organic light emitting diodes, solar cells and the like.

Description

Technical Field

[0001] The invention relates to the technical field of conjugated microporous polymer (CMPs) synthesis, in particular to two alkyne-containing conjugated microporous polymers with the same synthesis principle and in a helical structure, as well as preparation methods and applications thereof. Background Art

[0002] Conjugated microporous polymers (CMPs) are a class of organic porous polymers. Compared with conventional conjugated polymers or porous materials, their molecular structure has both a π-conjugated skeleton and a large number of micropores. As an emerging material platform, CMPs combine the advantages of a conjugated skeleton and micropores, and also have a large specific surface area, excellent chemical stability and good thermal stability. They have shown great potential in solving energy and environmental problems, and have shown great application prospects in many fields such as gas adsorption, heterogeneous catalysis, luminescent materials, chemical sensors, power storage and biohybrids.

[0003] At present, a variety of new methods for the design and synthesis of CMPs structural units have been developed in the existing technology to prepare a variety of CMPs with different structures and specific properties, which effectively promoted the rapid development of this field. In the synthesis process of CMPs, it is usually necessary to use a trifurcated central molecule as the core (Core) and a linear group molecule as a linker (Linker). The core molecule and the linker molecule are covalently connected through a π conjugated bond by a synthetic reaction to construct a conjugated skeleton.

[0004] The defects of this traditional method are: 1. The raw material structure is single, resulting in a conventional structure of the synthesized CMPs, which is limited in use and material performance; 2. There are many by-products in the reaction, resulting in 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 that they have novel structures, simple process steps, mild reaction conditions, and high product purity is of great significance for improving the development and application of conjugated microporous polymer materials. Summary of the invention

[0006] The technical purpose of the present invention is to provide two helical-structured alkyne-containing conjugated microporous polymers and a preparation method thereof, which start from designing reaction raw materials with high energy matching and good mutual selectivity, and construct them into functionalized conjugated microporous polymers with novel structures through Sonogashira coupling reaction. The present invention has the advantages of simple process steps, mild reaction conditions, high efficiency, good selectivity, novel structure of finished CMPs, high yield, good purity, etc., and has potential application value in the fields of optoelectronic equipment and the like.

[0007] To achieve the above object, the technical solution adopted by the present invention is: a conjugated microporous polymer containing alkyne groups in a helical structure, the structural formula of the conjugated microporous polymer is:

[0008] The method for preparing a helical structured alkyne-containing conjugated microporous polymer comprises the following steps: Take TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene as reaction raw materials, take CuI and tetrakis(triphenylphosphine)palladium as reaction aids, and dissolve them together in a pressure tube filled with triethylamine and anhydrous toluene. Then, place the obtained reaction system in an oil bath pot at 60-90°C for stirring reaction for 12-24 hours. After the reaction is completed, stand aging, suction filtration and washing are carried out in sequence, and then Soxhlet extraction is carried out with methanol for 20-30 hours. After vacuum freeze drying and grinding, loose dark brown powder target products CMP-1 and dark brown powder target products CMP-2 are obtained.

[0009] 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).

[0010] 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.

[0011] Preferably, the reaction temperature of the reaction system is 80° C. and the reaction time is 12 h.

[0012] Preferably, the reaction system is subjected to a freeze-thaw cycle degassing treatment before the stirring reaction.

[0013] Preferably, the static aging time is 10-15 hours.

[0014] Preferably, the reaction product is washed with DMF, water and acetone in sequence, and washing with each detergent is repeated 1-3 times. The Soxhlet extraction time is 24 hours, and the vacuum freeze drying time is 12 hours.

[0015] Preferably, the preparation method of anhydrous toluene is: adding sodium silk as a desiccant to toluene, using benzophenone as an indicator, and after the color of the toluene solution changes to purple, distilling it by atmospheric distillation, and collecting the fraction at 110° C. to obtain anhydrous toluene.

[0016] Applications of helical alkyne-containing conjugated microporous polymers in chiral recognition and separation, optical sensors, organic field-effect transistors and organic solar cells. Beneficial effects:

[0017] 1. The preparation process of the present invention 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. Through structural optimization and modular design of the target CMPs, two conjugated microporous polymers CMP-1 and CMP-2 are prepared by a solvothermal method based on the Sonogashira coupling reaction mechanism. It has the characteristics of novel raw material structure, simple synthesis process and low cost, mild reaction conditions, high yield, etc. The synthesized CMP-1 and CMP-2 have an extended π electron system, which makes them show good electronic conduction performance. These materials have potential application value in optoelectronic devices, such as organic light-emitting diodes, solar cells, etc.

[0018] 2. The CMP-1 and CMP-2 synthesized in the present invention both have a helical structure, which can cause the conjugated system of the polymer to produce special optical activity, such as circular dichroism and optical rotation, and can be used in the fields of chiral recognition and separation, optical sensors, etc. 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, allowing electrons to be transmitted more efficiently therein, so the present invention has potential application value in organic electronic devices, such as organic field effect transistors, organic solar cells, etc.

[0019] 3. The synthesis process of the present invention selects TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene for matching in raw material selection. When the TNP-3Br used in the raw material reacts with acetylene-containing benzene, the electron energy in the HOMO orbital of the acetylene-containing benzene is relatively high and relatively active. The carbon-bromine bond connected to the bromine atom in TNP-3Br has a certain polarity, resulting in a relatively low LUMO orbital energy of the carbon atom. The orbital energy of the two is well matched, so that the reaction can proceed smoothly under milder conditions, reducing the activation energy of the reaction, improving the efficiency and selectivity of the reaction, and thus improving the yield and purity of the finished CMPs.

[0020] 4. The solvent thermal reaction process of the present invention is carried out in a pressure tube. Compared with conventional reaction vessels, the pressure tube can allow reactions that originally require higher temperatures under normal pressure to be carried out at relatively low temperatures and high pressures, which is beneficial to improving reaction selectivity and yield and reducing the occurrence of side reactions. At the same time, the pressure tube is easy to operate and the process is simple.

[0021] 5. The synthesis process of the present invention uses anhydrous toluene as a reaction reagent. The preparation method of the anhydrous toluene is as follows: sodium silk is added to toluene as a desiccant, benzophenone is used as an indicator, blue indicates the absence of oxygen, purple indicates the absence of water, the color becomes darker, and it is distilled at normal pressure, and the fraction at 110° C. is collected. The anhydrous toluene greatly improves the anhydrous environment of the experiment and further reduces the occurrence of side reactions.

[0022] 6. The synthesis process of the present invention uses vacuum freeze drying to dehydrate the product. The advantage is that compared with traditional air drying, water can be directly sublimated from the solid state to the gaseous state (i.e., freeze drying process) under vacuum conditions, or quickly removed by direct evaporation of the liquid, which greatly shortens the entire drying cycle. Since the drying process is carried out at low temperature, the color, smell and microporous structure of the raw materials can be better 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 THE DRAWINGS

[0023] Figure 1 This is an infrared spectrum of the CMPs material synthesized in Example 1 of the present invention; Figure 2 This is a scanning electron microscope image of the CMP-1 material synthesized in Example 1 of the present invention; Figure 3 This is a scanning electron microscope image of the CMP-2 material synthesized in Example 1 of the present invention; Figure 4 This is a nitrogen adsorption desorption diagram of the CMP-1 material synthesized in Example 1 of the present invention; Figure 5 This is a pore size diagram of the CMP-1 material synthesized in Example 1 of the present invention; Figure 6 This is a nitrogen adsorption and desorption diagram of the CMP-2 material synthesized in Example 1 of the present invention. DETAILED DESCRIPTION

[0024] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments: The present invention provides two helical-structured alkyne-containing conjugated microporous polymers and synthesis methods thereof. The synthesis principles of the two helical-structured alkyne-containing conjugated microporous polymers are the same, wherein the synthesis of CMP-1 is as follows: According to the molar ratio of 2:(2-4), the reaction raw materials TNP-3Br and 1,4-diethynylbenzene are taken, CuI and tetrakis(triphenylphosphine)palladium are used as catalysts, and they are dissolved together in a pressure tube filled with triethylamine and toluene; the obtained mixed solution is subjected to freeze-thaw cycle degassing treatment, and then placed in an oil bath pot at 60-90°C for stirring reaction for 12-24 hours; after the reaction is completed, it is allowed to stand and age for 10-15 hours, and then filtered. The product is washed and filtered with DMF, water, and acetone for multiple times, and then Soxhlet extraction is performed with methanol for 20-30 hours. Finally, vacuum freeze-drying is performed for 12 hours, and a dark brown powder is obtained after grinding, which is the target product CMP-1.

[0025] The reaction formula is as follows:

[0026] The synthesis of CMP-2 is as follows:

[0027] According to the molar ratio of 2:(1-3), the reaction raw materials TNP-3Br and 1,3,5-triethynylbenzene are taken, CuI and tetrakis(triphenylphosphine)palladium are used as catalysts, and they are dissolved together in a pressure tube filled with triethylamine and toluene; the obtained mixed solution is subjected to freeze-thaw cycle degassing treatment, and then placed in an oil bath pot at 60-90°C for stirring reaction for 12-24 hours; after the reaction is completed, it is allowed to stand and age for 10-15 hours, and then filtered. The product is washed and filtered with DMF, water, and acetone for multiple times. After washing, it is extracted with methanol for Soxhlet extraction for 20-30 hours, and finally vacuum freeze-dried for 12 hours. After grinding, a dark brown powder can be obtained, which is the target product CMP-2.

[0028] The reaction formula is as follows:

[0029] The structural characteristics and features of the conjugated microporous polymers CMP-1 and CMP-2 synthesized by the present invention are: The present invention 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 adopts a solvothermal method to prepare two conjugated microporous polymers CMP-1 and CMP-2. The present invention has the characteristics of novel raw material structure, simple synthesis process and low cost, mild reaction conditions, high yield, etc. The synthesized CMP-1 and CMP-2 have an extended π electron system, so that they exhibit good electronic conduction performance. These materials have potential application value in optoelectronic devices, such as organic light emitting diodes, solar cells, etc., and have good application prospects.

[0030] Example 1 The specific preparation steps of the preparation process of this embodiment are: 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 filled with triethylamine (2 ml) and anhydrous toluene (2 ml). The mixture was 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. After standing and aging for 12 hours, it was filtered. The product was first washed with DMF to remove unreacted TNP-3Br, 1,4-diethynylbenzene, tetrakis(triphenylphosphine palladium) and CuI. The DMF molecules remaining on the surface and in the pores of the sample were washed with double distilled water. Finally, the oligomers and impurities were washed with acetone. After washing, Soxhlet extraction was performed with methanol for 24 h, and vacuum freeze-dried for 12 h. After the material was fully ground, dark brown powder CMP-1 and dark brown powder CMP-2 products were obtained.

[0031] The results show that the yield of CMP-1 and CMP-2 obtained in this embodiment is 73.2%, and the specific surface area of ​​the product is 270.83 m 2 / g, pore size is 1.59nm, Langmuir specific surface area is 462.23m 2 / g; the yield of CMP-2 is 68.3% (because the molecular size of 1,3,5-triethynylbenzene is smaller than that of TNP-3Br, it is more difficult to combine, so the yield is reduced), and the specific surface area of ​​the product is 261.46m 2 / g, pore diameter is 1.59nm, Langmuir specific surface area is 440.37m 2 / g.

[0032] Example 2 Keeping other conditions unchanged in Example 1, and increasing the proportion of acetylene group ligands (the molar ratio of TNP-3Br to 1,4-diethynylbenzene in the raw material is 2:3.5, and the molar ratio of TNP-3Br to 1,3,5-triethynylbenzene is 2:2.5), the specific surface area of ​​the product will be slightly larger. This is because the bromine group ligand can fully react with the excess acetylene group-containing ligand, and the unreacted acetylene group ligand is easier to separate from the reaction product, making the polymer irregular. Therefore, the ratio of the amount of TNP-3Br and 1,4-diethynylbenzene (1,3,5-triethynylbenzene) can be appropriately adjusted, preferably the molar ratio of TNP-3Br to 1,4-diethynylbenzene in the reaction raw material is 2:3, and the molar ratio of TNP-3Br to 1,4-diethynylbenzene is 2:2.

[0033] Example 3 When the other conditions in Example 1 are kept unchanged and the amount of anhydrous toluene is reduced to 1 ml, the concentration of the base increases, which reduces the activity of the catalyst and is not conducive to the reaction. Therefore, the amount of toluene should be maintained at 2-2.5 ml.

[0034] Example 4 Keeping other conditions unchanged in Example 1, the reaction solvent anhydrous toluene was replaced with anhydrous N,N'-dimethylformamide (DMF), and it was found that the color of the reactant was black. It was determined that in addition to a small amount of product, a large amount of black impurities were also generated. Analysis showed that DMF has strong hygroscopicity and easily absorbs moisture in the air, destroying the anhydrous environment of the reaction. Therefore, the reaction should be carried out in anhydrous toluene solvent.

[0035] Example 5 When other conditions in Example 1 are kept unchanged and triethylamine is replaced with anhydrous potassium carbonate, it is found that the reaction is basically not carried out. It is known that anhydrous potassium carbonate is basically insoluble in toluene, and the reaction is difficult to react or even does not react without the participation of a base. Generally speaking, organic bases are conducive to polymer polymerization reactions, so triethylamine is relatively more suitable as a base for the reaction.

[0036] Example 6 When other conditions in Example 1 are kept unchanged and the reaction temperature is increased to 100°C, it is found that the reaction is completed more quickly, but as the reaction proceeds further, the product will appear dark brown and there will be little precipitate. It has been determined that the yield is greatly reduced because the thermal motion of the molecules will increase at a higher temperature, thereby accelerating the collision frequency and energy transfer between reactions, and destroying the structure of the generated product. Therefore, the reaction temperature should be controlled at 60-90°C.

[0037] Example 7 When other conditions in Example 1 remain unchanged and the reaction time is increased to 48h, it is found that the reaction product is dark brown and has less precipitate, which is consistent with the phenomenon in Example 6. It is determined that its specific surface area is small. This is because the microporous structure has been well formed after 12h of reaction. As the reaction time increases, the already formed microporous structure will undergo irreversible deformation, changing the morphological characteristics of the molecules. Therefore, the reaction time should be controlled within 12-24h.

[0038] Example 8 While keeping other conditions in Example 1 unchanged, the pressure tube was replaced with a reactor for reaction. It was found that the experimental operation was extremely inconvenient. This is because the amount of sample required for this experiment is small, and the pressure tube is easier to perform the experimental operation. The pressure tube has a larger surface area to volume ratio, which helps to improve the heat exchange efficiency and make temperature control more precise and rapid.

[0039] Example 9 While keeping other conditions in Example 1 unchanged, freeze drying was replaced by heating drying. It was found under an electron microscope that the morphology of the product partially collapsed. This was because the high temperature destroyed the microstructure of the product. The freeze drying process did not cause the molecules to be destroyed, and the original form and microstructure of the material could be better maintained. Freeze drying could remove most of the bound water in the material, and the residual moisture in the final product was usually less than 5%, which is particularly beneficial for products that need to be stored for a long time.

[0040] In the above embodiments, brown powder begins to adhere to the wall of the reaction container after about 3 hours of reaction. To avoid too slow reaction, the temperature can be appropriately raised to 80°C. Analysis and characterization of finished helical-structured alkyne-containing conjugated microporous polymer materials:

[0041] The performance of CMP-1 and CMP-2 synthesized in Example 1 of the present invention was analyzed.

[0042] FT-IR analysis: Figure 1 The FT-IR diagrams of the bromine-containing intermediate and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene used as raw materials in the present invention, and CMP-1 and CMP-2 synthesized therefrom. Figure 1 The lines in the figure include three solid lines and two dotted lines from top to bottom, namely, the first solid line in the upper part, the first dotted line in the upper part, the second solid line in the middle part, the second dotted line in the lower part, and the third solid line in the lower part. The first solid line in the upper part is the infrared spectrum line of 1,4-diethynylbenzene, 3250cm -1 The peak at 550 cm-1 is attributed to the stretching vibration of the C-H bond. -1 and 498cm -1 The peak at 943 cm is attributed to the bending vibration of the C≡C bond; the second solid line in the middle is the infrared spectrum line of the bromine-containing intermediate, 943 cm -1 and 533cm -1 The two groups of peaks at are caused by the stretching vibration and bending vibration of C-Br; the first dotted line on the top is the infrared spectrum of CMP-1. Figure 1 The strong bands indicated by the shaded part in the middle can be inferred that the characteristic peaks on the infrared spectra of the raw material 1,4-diethynylbenzene and the bromine-containing intermediate are both reflected in the product CMP-1, which can prove the integrity of the product. When the Br on the C-Br bond couples with the alkynyl group and leaves, correspondingly, the first solid line at 3250cm -1 , 943cm on the second solid line in the middle -1 and 533cm -1 The peak at disappears on the first upper dashed line, proving the successful synthesis of CMP-1.

[0043] Figure 1 The third solid line in the lower middle part is the infrared spectrum line of 1,3,5-triethynylbenzene, 3277cm -1 The peak at 672 cm is attributed to the stretching vibration of the C-H bond. -1 and 613cm -1 The peak at 943 cm is attributed to the bending vibration of the C≡C bond; the second solid line in the middle is the infrared spectrum line of the bromine-containing intermediate, 943 cm -1 and 533cm -1 The two groups of peaks at are caused by the stretching vibration and bending vibration of C-Br; the second dotted line at the bottom is the infrared spectrum of CMP-2. Figure 1 The strong bands indicated by the shaded part in the middle can be inferred that the characteristic peaks on the infrared spectra of the raw material 1,3,5-triethynylbenzene and the bromine-containing intermediate are both reflected in the product CMP-2, which can prove the integrity of the product. When the Br on the C-Br bond couples with the alkynyl group and leaves, the corresponding peak on the first solid line at 3277cm -1 , 943cm on the second solid line in the middle -1 and 533cm -1 The peak at disappears on the first upper dashed line, proving the successful synthesis of CMP-2.

[0044] Scanning electron microscopy analysis: Scanning electron microscopy (SEM) is a method between transmission electron microscopy and optical microscopy for observing the morphology and composition of the ultrastructure of solid surfaces. It uses a narrowly focused high-energy electron beam to scan the sample, and stimulates various physical information through the interaction between the beam and the material. When the scanning electron beam interacts with the sample, a variety of signals are generated, including secondary electrons, absorbed electrons, Auger electrons, backscattered electrons and X-rays, among which the most important are secondary electrons. Scanning electron microscopes generally use electron beams to scan the surface of the sample, and then collect the generated secondary electrons with a special detector, form electrical signals and transport them to the cathode ray tube, and finally display the morphology of the object on the fluorescent screen. This information is collected, amplified, and re-imaged to achieve the purpose of characterizing the microscopic morphology of the material.

[0045] Figure 2 , Figure 3 They are scanning electron microscope images of two materials synthesized in Example 1 of the present invention, and the microscopic morphology of the synthesized conjugated microporous materials is observed. Figure 2 , Figure 3 Scanning electron microscope photos show that the particles of materials CMP-1 and CMP-2 are of different sizes, with a relatively rough surface and uniform pores. The particle size is about 1 to 3 microns, and they are spherical in shape. There are no ribbons, fibers or rods, and there is a certain degree of agglomeration.

[0046] Nitrogen adsorption and desorption curve analysis: Figure 4 Nitrogen for CMP-1 at 77K (pore size ) Adsorption-desorption isotherms, the hollow circles are desorption isotherms, and the 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 research process, after determining the structure of the organic porous material, it is necessary to characterize its pore size characteristics and specific surface area and other properties. The operation is as follows: First, the sample powder is fully ground. In order to remove the guest solvent molecules in the skeleton pores, it is necessary to place it in a vacuum dryer at 100°C for 12 hours before the test. Then, a nitrogen adsorption-desorption test experiment is carried out on CMP-1 at 77K. It is found that the product has a typical type I gas adsorption curve, indicating that there is a microporous structure in CMP-1. Analysis Figure 4 It was found that the adsorption curve rose slowly and the desorption curve lagged. References show that this phenomenon is caused by the unique swelling characteristics of the organic skeleton. The BET model specific surface area of ​​CMP-1 is 270.83 m 2 ·g -1 The Langmuir specific surface area is 462.23 m 2 ·g -1 According to the density pan-enthalpy theory (DFT) model analysis, the pore size distribution of the microporous material is uniform.

[0047] Figure 6 Nitrogen for CMP-2 at 77K (pore size ) adsorption-desorption isotherm, the hollow circle is the desorption isotherm, and the solid circle is the adsorption isotherm. In the research process, after determining the structure of the organic porous material, it is necessary to characterize its pore size characteristics and specific surface area and other properties. The operation is as follows: First, the sample powder is fully ground. In order to remove the guest solvent molecules in the skeleton pores, it is necessary to place it in a vacuum dryer at 100°C for 12 hours before testing. Then, a 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, indicating the presence of a microporous structure in CMP-1. Analysis Figure 6 It was found that the adsorption curve rose slowly and the desorption curve lagged. References show that this phenomenon is caused by the unique swelling characteristics of the organic skeleton. The BET model specific surface area of ​​CMP-2 is 261.46 m 2 ·g -1 The Langmuir specific surface area is 440.37 m 2 ·g -1 According to the density pan-enthalpy theory (DFT) model analysis, the pore size distribution of the microporous material is uniform.

[0048] 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 containing alkyne groups in a helical structure, characterized in that: The structural formula of the conjugated microporous polymer is:

2. The method for preparing the alkyne-containing conjugated microporous polymer having a helical structure according to claim 1, characterized in that: The following steps are involved: Take TNP-3Br and 1,4-diethynylbenzene or 1,3,5-triethynylbenzene as reaction raw materials, take CuI and tetrakis(triphenylphosphine)palladium as reaction aids, and dissolve them together in a pressure tube filled with triethylamine and anhydrous toluene. Then, place the obtained reaction system in an oil bath pot at 60-90°C for stirring reaction for 12-24 hours. After the reaction is completed, stand aging, suction filtration and washing are carried out in sequence, and then Soxhlet extraction is carried out with methanol for 20-30 hours. After vacuum freeze drying and grinding, loose dark brown powder target products CMP-1 and dark brown powder target products CMP-2 are obtained.

3. The method for preparing the alkyne-containing conjugated microporous polymer with a helical structure according to claim 2, characterized in that: 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).

4. The method for preparing the alkyne-containing conjugated microporous polymer with a helical structure according to claim 3, characterized in that: 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.

5. The method for preparing the alkyne-containing conjugated microporous polymer with a helical structure according to claim 2, characterized in that: The reaction temperature of the reaction system is 80° C. and the reaction time is 12 h.

6. The method for preparing the alkyne-containing conjugated microporous polymer with a helical structure according to claim 2, characterized in that: The reaction system needs to be degassed by freeze-thaw cycle before stirring the reaction.

7. The method for preparing the alkyne-containing conjugated microporous polymer with a helical structure according to claim 2, characterized in that: The static aging time is 10-15h.

8. The method for preparing the alkyne-containing conjugated microporous polymer with a helical structure according to claim 2, characterized in that: The reaction product was washed with DMF, water and acetone in sequence, and each washing agent was repeated 1-3 times. The Soxhlet extraction time was 24 hours, and the vacuum freeze drying time was 12 hours.

9. The method for preparing the alkyne-containing conjugated microporous polymer having a helical structure according to claim 2, characterized in that: The preparation method of anhydrous toluene is as follows: sodium silk is added to toluene as a desiccant, benzophenone is used as an indicator, and after the color of the toluene solution changes to purple, it is distilled by atmospheric distillation, and the fraction at 110° C. is collected to obtain anhydrous toluene.

10. Use of the alkyne-containing conjugated microporous polymer with a helical structure according to claim 1 in chiral recognition and separation, optical sensors, organic field effect transistors and organic solar cells.

Images