A CuTEP-PPV-COF polymer and its preparation method and application

Abstract

The present invention relates to the technical field of porous organic polymer materials, specifically to a CuTEP-PPV-COF polymer, a preparation method thereof, and its use as a catalyst in the synthesis of benzyl alcohol into benzaldehyde. When the CuTEP-PPV-COF polymer provided by the present invention is used as the main catalyst and tetramethylpiperidinium oxide (TEMPO) as a co-catalyst to catalyze the synthesis of benzyl alcohol into benzaldehyde, the yield can reach as high as 99%. Furthermore, after six cycles of reaction, the CuTEP-PPV-COF polymer still maintains a catalytic yield of over 95%, demonstrating that the CuTEP-PPV-COF polymer provided by the present invention has efficient and stable catalytic performance and can be recycled multiple times. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the technical field of porous organic polymer materials, and in particular to a CuTEP-PPV-COF polymer, a preparation method thereof, and application of the CuTEP-PPV-COF polymer as a catalyst in catalyzing the synthesis of benzyl alcohol into benzaldehyde. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] Benzaldehyde is a widely used chemical intermediate in industries such as pharmaceuticals and pesticides. Its preparation methods primarily include the toluene oxidation method and the benzyl alcohol oxidation method. Compared to toluene, benzyl alcohol is less toxic, less expensive, and more efficient, making the benzyl alcohol oxidation method the most viable method for producing benzaldehyde. Traditional benzyl alcohol oxidation reactions, using permanganate and dichromate as oxidants, not only produce large amounts of environmentally unfriendly heavy metal waste but also suffer from poor selectivity. Consequently, chemists have developed numerous catalytic oxidation methods using metals as catalysts and molecular oxygen as oxidants to avoid the use of toxic strong oxidants, providing a green approach for the selective oxidation of benzyl alcohol.

[0004] However, among the reported catalytic oxidation methods, most are homogeneous reactions, and the catalysts cannot be recycled and reused, which easily causes pollution and waste. Compared with homogeneous catalysis, heterogeneous catalysis has the advantages of stable and recyclable catalysts, which is more in line with the requirements of sustainable synthetic chemistry. However, the existing disclosed heterogeneous catalytic technology often requires the use of precious metals such as Ru, Pt, Pd, Au, Rh, etc. as catalysts, and the catalyst synthesis steps are complicated, making it difficult to achieve large-scale industrial production.

[0005] Covalent organic framework materials (COFs), as an emerging porous crystalline polymer in two-dimensional conjugated network materials, have size-adjustable nanopores, high specific surface area, good chemical stability and uniformly dispersed catalytic active sites. Therefore, they have good development prospects in the field of catalytic oxidation of benzyl alcohol. Summary of the Invention

[0006] In order to overcome the above problems, the present invention provides a CuTEP-PPV-COF polymer, a preparation method thereof, and use thereof as a catalyst in catalyzing the synthesis of benzyl alcohol into benzaldehyde.

[0007] In order to achieve the above technical objectives, the present invention adopts the following technical solutions:

[0008] The first aspect of the present invention provides a CuTEP-PPV-COF polymer, the structural formula of which is shown in formula (I):

[0009]

[0010] A second aspect of the present invention provides a method for preparing the above-mentioned CuTEP-PPV-COF polymer, comprising:

[0011] The ligands 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP) and 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3) were dispersed in a mixed solution of dimethyl sulfoxide (DMSO) and water. Sodium ascorbate and anhydrous copper sulfate were then added as catalysts. The mixed solution was placed in a liquid nitrogen bath and subjected to freeze-thaw and cyclic degassing. After sealing, a solvothermal reaction was carried out to obtain the CuTEP-PPV-COF polymer.

[0012] The reaction process is:

[0013]

[0014] The third aspect of the present invention provides use of the above-mentioned CuTEP-PPV-COF polymer as a catalyst.

[0015] The beneficial effects of the present invention are:

[0016] (1) The CuTEP-PPV-COF polymer prepared in the present invention has high crystallinity, large porosity, and good chemical stability, and therefore has the potential to be used as a catalyst.

[0017] (2) When the CuTEP-PPV-COF polymer provided by the present invention was used as the primary catalyst and tetramethylpiperidinium oxide (TEMPO) as the co-catalyst to catalyze the synthesis of benzaldehyde from benzyl alcohol, the yield reached as high as 99%. Furthermore, after six cycles of reaction, the CuTEP-PPV-COF polymer maintained a catalytic yield exceeding 95%. This demonstrates that the CuTEP-PPV-COF polymer provided by the present invention has efficient and stable catalytic performance and can be recycled multiple times.

[0018] (3) The CuTEP-PPV-COF polymer provided by the present invention is used as a catalyst for the oxidation reaction of benzyl alcohol. The catalyst is inexpensive, has high yield and purity, is easy to separate, no special, toxic or harmful reagents are used during the experiment, and the reaction conditions are mild. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0020] Figure 1 This is a scanning electron micrograph of the CuTEP-PPV-COF prepared in Example 3 of the present invention;

[0021] Figure 2 This is the thermogravimetric diagram of CuTEP-PPV-COF prepared in Example 3 of the present invention;

[0022] Figure 3 The experimental and simulated PXRD patterns of CuTEP-PPV-COF prepared in Example 3 of the present invention;

[0023] Figure 4 This is the N2 adsorption graph of CuTEP-PPV-COF prepared in Example 3 of the present invention;

[0024] Figure 5 This is the PXRD pattern of the CuTEP-PPV-COF prepared in Example 3 of the present invention after catalysis for 5 times. DETAILED DESCRIPTION

[0025] It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0026] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0027] A first typical embodiment of the present invention provides a CuTEP-PPV-COF polymer, the structural formula of which is shown in formula (I):

[0028]

[0029] A second typical embodiment of the present invention provides a method for preparing the above-mentioned CuTEP-PPV-COF polymer, comprising:

[0030] The ligands 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP) and 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3) were dispersed in a mixed solution of dimethyl sulfoxide (DMSO) and water. Sodium ascorbate and anhydrous copper sulfate were then added as catalysts. The mixed solution was placed in a liquid nitrogen bath and subjected to freeze-thaw and cyclic degassing. After sealing, a solvothermal reaction was carried out to obtain the CuTEP-PPV-COF polymer.

[0031] The reaction process is:

[0032]

[0033] In one or more embodiments, the molar ratio of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP) to 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3) is 1:1.8-2.2, preferably 1:2.

[0034] In one or more embodiments, in the mixed solution of dimethyl sulfoxide and water, the volume ratio of dimethyl sulfoxide to water is 1.8 to 2.2:1, preferably 2:1.

[0035] In one or more embodiments, the concentration of the ligand copper 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin (CuTEP) in a mixed solution of dimethyl sulfoxide (DMSO) and water is 2 to 4 mmol / L, preferably 3 mmol / L.

[0036] In one or more embodiments, the molar ratio of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP) and sodium ascorbate to anhydrous copper sulfate is 5:0.8-1.2:0.8:-1.2, preferably 5:1:1.

[0037] In one or more embodiments, the temperature of the solvothermal reaction is 110-130° C., preferably 120° C.; the time of the solvothermal reaction is 90-100 h, preferably 94 h.

[0038] In one or more embodiments, the preparation method of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP) includes:

[0039] (1) Compound 1 was dissolved in dichloromethane, and then pyrrole and boron trifluoride ether were added. After the reaction was allowed to react at room temperature for 2 to 4 hours, tetrachlorobenzoquinone was added and the reaction was allowed to proceed at 35 to 45°C for 0.5 to 2 hours. After the reaction was completed, the solvent was removed and the compound 2 was obtained after purification.

[0040] (2) Compound 2 and tetrabutylammonium fluoride were added to tetrahydrofuran and reacted at room temperature for 2 to 4 hours. After the reaction, water was added, the filtrate was collected by filtration, the solvent was removed, and the compound 3 was obtained after drying.

[0041] (3) Copper acetate was dissolved in methanol and added to dichloromethane together with compound 3. The mixture was stirred at room temperature for 10 to 15 hours. After the reaction, dichloromethane extraction, sodium bicarbonate solution washing, dehydration and drying were carried out in sequence, and then rotary evaporation and drying were carried out to obtain 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP).

[0042] The reaction process is:

[0043]

[0044] In one or more embodiments, the preparation method of 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3) comprises:

[0045] (1) Under N2 atmosphere, 1,4-diiodobenzene, 18-crown ether-6, 1,6-dibromohexane and K2CO3 were added to acetone and reacted at 75-85°C for 70-80 hours. After the reaction was completed, deionized water was added to quench the reaction, and the product was extracted with dichloromethane. The organic phase was collected, the solvent was removed, and 1,4-bis[(6-bromohexyl)oxy]-2,5-diiodobenzene (PPV-Br) was obtained after purification.

[0046] (2) PPV-Br and sodium azide are added to a mixed solution of N,N-dimethylacetamide, dichloromethane and water, and the mixture is reacted at 85-95°C for 10-14 hours. After the reaction is completed, the mixture is cooled to room temperature, ice water is added to the reaction solution, and the solid obtained by filtration is 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3);

[0047] The reaction process is:

[0048]

[0049] Preferably, in step (1), the molar ratio of 1,4-diiodobenzene, 18-crown-6, 1,6-dibromohexane and K2CO3 is 9-11:0.9-1.1:155-170:50-60, preferably 10:1:160:54.

[0050] Preferably, in step (2), the molar ratio of PPV-Br to sodium azide is 1:8 to 12, preferably 1:10.

[0051] The third aspect of the present invention provides use of the above-mentioned CuTEP-PPV-COF polymer as a catalyst.

[0052] In one or more embodiments, the application includes catalyzing the synthesis of benzyl alcohol into benzaldehyde.

[0053] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0054] Example 1

[0055] Preparation of ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP):

[0056] (1) Compound 1 (4.0 mmol, 810 mg) was weighed and placed in a 500 mL three-necked flask. Dichloromethane (350 mL) was added, and pyrrole (4.0 mmol, 280 μL) and boron trifluoride etherate (0.9 mmol, 140 μL) were added dropwise. After stirring at room temperature for 3 h, tetrachlorobenzoquinone (3.1 mmol, 760 mg) was added and stirred at 40°C for 1 h. After the reaction, the reaction solution turned from brown to black. The solution was dried by rotary evaporation and purified by column chromatography to obtain compound 2.

[0057] (2) Compound 2 (1.0 mmol, 670 mg) was weighed and placed in a 100 mL flask. Tetrabutylammonium fluoride (1.5 mL) and tetrahydrofuran (40 mL) were added and stirred at room temperature for 3 h. After the reaction was completed, the filtrate was collected, rotary evaporated, and dried to obtain compound 3.

[0058] (3) Copper acetate (0.74 mmol, 147 mg) was dissolved in 70 mL of methanol and placed in a 250 mL flask along with compound 3 (0.075 mmol, 53 mg). Dichloromethane (30 mL) was added and the mixture was stirred at room temperature for 12 h. After the reaction, the solvent was evaporated in vacuo. The product was extracted with dichloromethane, washed with 10% NaHCO3 solution, and dried over anhydrous MgSO4. After filtration, the product was rotary evaporated and dried in vacuo to obtain the product. Ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP) was obtained.

[0059] The reaction process is:

[0060]

[0061] Example 2

[0062] Preparation of 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3):

[0063] (1) Under N2 atmosphere, 1,4-diiodobenzene (2.5 mmol, 0.9 mg), 18-crown-6 (0.25 mmol, 72.8 mg), and K2CO3 (13.5 mmol, 1.4 mg) were added to a 100 mL flask, and 1,6-dibromohexane (40.0 mmol, 10.0 g) and 25 mL of acetone were added. The mixture was reacted at 80°C for 72 h. After the reaction was completed, 25 mL of H2O was added to quench the reaction. The product was extracted with dichloromethane and dried over anhydrous magnesium sulfate. The solvent was removed in vacuo, and dichloromethane / petroleum ether (1:5) was used as the eluent to obtain a white solid, 1,4-bis[(6-bromohexyl)oxy]-2,5-diiodobenzene (PPV-Br).

[0064] (2) PPV-Br (0.3 mmol, 200.0 mg) and sodium azide (3.0 mmol, 195.0 mg) were placed in a 50 mL flask, and 7.5 mL of DMF, 2 mL of CH2Cl2, and 2 mL of H2O were added. The mixture was reacted at 90°C for 12 h. After the reaction was completed, the mixture was cooled to room temperature and ice water was added to the reaction solution. A white crystalline solid precipitated and was filtered to obtain the solid. The solid was first washed with water and then washed three times with anhydrous ethanol. The solid was naturally dried to obtain a white crystalline product, namely 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3).

[0065] The reaction process is:

[0066]

[0067] Example 3

[0068] Preparation of CuTEP-PPV-COF polymer:

[0069] The ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP) (0.01 mmol, 8.0 mg) and 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene (PPV-N3) (0.02 mmol, 12.24 mg) prepared in Example 1 were placed in a pressure-resistant glass tube, and sodium ascorbate (0.002 mmol, 0.3 mg) and anhydrous copper sulfate (0.002 mmol, 0.32 mg) were added as catalysts. 3 mL of an aqueous solution of dimethyl sulfoxide (2:1 by volume) was added, and the mixed solution was placed in a liquid nitrogen bath for freeze-thaw and degassing three times. After sealing, it was placed in an oven and programmed to rise from room temperature to 120°C within 24 hours. After reacting at 120°C for 96 hours, heating was stopped. After the oven temperature dropped to room temperature, the solid in the glass tube was taken out, and washed thoroughly with DMF, H2O, and tetrahydrofuran (THF), respectively, and then dried in vacuo to obtain a red crystalline powder, which was the product CuTEP-PPV-COF.

[0070] The CuTEP-PPV-COF polymer prepared in this example was characterized. Figure 1 is the scanning electron microscope image of CuTEP-PPV-COF polymer. Figure 2 Thermogravimetric image of CuTEP-PPV-COF polymer. Figure 3 is the PXRD pattern of CuTEP-PPV-COF polymer, Figure 4 This is the N2 adsorption image of CuTEP-PPV-COF polymer. Figure 1 、 Figure 3 and Figure 4 It can be seen from the above that the CuTEP-PPV-COF polymer prepared in this embodiment has a porous structure. Figures 2 and 3 It can be seen that the CuTEP-PPV-COF polymer is a crystalline porous material with high thermal stability.

[0071] Experimental Example 1

[0072] The CuTEP-PPV-COF polymer prepared in Example 3 of the present invention was used as a catalyst to catalyze the oxidation reaction of benzyl alcohol.

[0073] The preparation process is as follows: benzyl alcohol (0.21 mmol, 20 μL), CuTEP-PPV-COF (1 mmol%, 0.01 mmol, 20.0 mg), and tetramethylpiperidinium oxide (Tempo) (1 mmol%, 0.01 mmol, 1.56 mg) are added to a 25 mL reaction flask. 2 mL of xylene is added as solvent. The reaction is carried out at 130°C for 30 hours. After the reaction is completed, the temperature is lowered to room temperature, and the CuTEP-PPV-COF is isolated by centrifugation. The reaction yield is determined by gas chromatography-mass spectrometry (GC-MS).

[0074] The specific reaction equation is as follows:

[0075]

[0076] The reaction was tracked by TLC. After the reaction was completed, the catalyst was recovered by centrifugation and directly put into the next cycle reaction. According to the above conditions, the catalyst was used for six cycles. The reaction solution was separated and the yield was calculated. The catalytic effect is shown in Table 1. Figure 5 The PXRD pattern of the catalyst after 5 cycles is shown in Figure 2. Figure 5 It can be seen that after five cycles of the catalyst, the CuTEP-PPV-COF framework remains unchanged. As can be seen from Table 1, the product yield remains essentially the same, showing only a slight downward trend after six cycles, reflecting the excellent stability of the catalyst. It can be reused more than six times, significantly improving catalyst utilization and reducing production costs.

[0077] Table 1 Catalytic effect of CuTEP-PPV-COF multiple cycle reactions

[0078]

[0079] When the CuTEP-PPV-COF polymer provided by the present invention is used as the main catalyst and tetramethylpiperidinium oxide (TEMPO) as a co-catalyst to catalyze the synthesis of benzaldehyde from benzyl alcohol, the yield can reach as high as 99%. Furthermore, after six cycles of reaction, the CuTEP-PPV-COF polymer still maintains a catalytic yield of over 95%. This demonstrates that the CuTEP-PPV-COF polymer provided by the present invention has efficient and stable catalytic performance and can be recycled multiple times.

[0080] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A CuTEP-PPV-COF polymer, characterized in that The structural formula is shown in formula (I): Formula (I).

2. The method for preparing the CuTEP-PPV-COF polymer according to claim 1, wherein include: The ligands 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper and 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene were dispersed in a mixed solution of dimethyl sulfoxide and water. Sodium ascorbate and anhydrous copper sulfate were then added as catalysts. The mixed solution was placed in a liquid nitrogen bath and subjected to freeze-thaw and cyclic degassing. After sealing, a solvothermal reaction was performed to obtain the CuTEP-PPV-COF polymer. The reaction process is: 。 3. The preparation method according to claim 2, wherein The molar ratio of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper to 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene is 1:1.8~2.

2.

4. The preparation method according to claim 3, wherein The molar ratio of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper and 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene is 1:

2.

5. The preparation method according to claim 2, wherein In the mixed solution of dimethyl sulfoxide and water, the volume ratio of dimethyl sulfoxide to water is 1.8~2.2:

1.

6. The preparation method according to claim 5, wherein The volume ratio of dimethyl sulfoxide to water is 2:

1.

7. The preparation method according to claim 2, wherein The concentration of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper in a mixed solution of dimethyl sulfoxide (DMSO) and water is 2~4 mmol / L.

8. The preparation method according to claim 7, wherein The concentration of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper in a mixed solution of dimethyl sulfoxide (DMSO) and water was 3 mmol / L.

9. The preparation method according to claim 2, wherein The molar ratio of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper and sodium ascorbate to anhydrous copper sulfate is 5:0.8~1.2:0.8:~1.

2.

10. The preparation method according to claim 9, characterized in that The molar ratio of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper and sodium ascorbate to anhydrous copper sulfate is 5:1:

1.

11. The preparation method according to claim 2, characterized in that The temperature of the solvothermal reaction is 110~130 ℃; the time of the solvothermal reaction is 90~100 h.

12. The preparation method according to claim 11, characterized in that The solvothermal reaction temperature was 120 °C and the solvothermal reaction time was 94 h.

13. The preparation method according to claim 2, wherein The preparation method of the ligand 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper comprises: (1) Compound 1 was dissolved in dichloromethane, and then pyrrole and boron trifluoride ether were added. After the reaction was carried out at room temperature for 2-4 h, tetrachlorobenzoquinone was added and the reaction was carried out at 35-45 °C for 0.5-2 h. After the reaction was completed, the solvent was removed and the compound 2 was obtained after purification. (2) Compound 2 and tetrabutylammonium fluoride were added to tetrahydrofuran and reacted at room temperature for 2-4 h. After the reaction, water was added and the filtrate was collected by filtration. The solvent was removed and dried to obtain compound 3. (3) Copper acetate was dissolved in methanol and added to dichloromethane together with compound 3. The mixture was stirred at room temperature for 10-15 hours. After the reaction, dichloromethane extraction, sodium bicarbonate solution washing, dehydration and drying were carried out in sequence. The mixture was then rotary evaporated and dried to obtain 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin copper (CuTEP). 。 14. The preparation method according to claim 2, wherein The preparation method of 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene comprises: (1) Under N2 atmosphere, 1,4-dihydroxy-2,5-diiodobenzene, 18-crown-6, 1,6-dibromohexane and K2CO3 were added to acetone and reacted at 75-85 °C for 70-80 h. After the reaction was completed, deionized water was added to quench the reaction, and the product was extracted with dichloromethane. The organic phase was collected, the solvent was removed, and 1,4-bis[(6-bromohexyl)oxy]-2,5-diiodobenzene (PPV-Br) was obtained after purification. (2) PPV-Br and sodium azide were added to a mixed solution of N,N-dimethylacetamide, dichloromethane and water, and the mixture was reacted at 85-95°C for 10-14 h. After the reaction was completed, the mixture was cooled to room temperature, ice water was added to the reaction solution, and the solid obtained by filtration was 1,4-bis[(6-azidohexyl)oxy]-2,5-diiodobenzene; The reaction process is: 。 15. The preparation method according to claim 14, wherein In step (1), the molar ratio of 1,4-dihydroxy-2,5-diiodobenzene, 18-crown-6, 1,6-dibromohexane and K2CO3 is 9~11:0.9~1.1:155~170:50~60.

16. The preparation method according to claim 15, characterized in that In step (1), the molar ratio of 1,4-dihydroxy-2,5-diiodobenzene, 18-crown-6, 1,6-dibromohexane and K2CO3 is 10:1:160:

54.

17. The preparation method according to claim 14, wherein In step (2), the molar ratio of PPV-Br to sodium azide is 1:8~12.

18. The preparation method according to claim 17, wherein The molar ratio of PPV-Br to sodium azide was 1:

10.

19. Use of the CuTEP-PPV-COF polymer according to claim 1 as a catalyst.

20. The use according to claim 19, characterized in that The application includes catalyzing the synthesis of benzaldehyde from benzyl alcohol.

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