A polyacetylenoid compound, its preparation method and application

Abstract

This invention discloses a polyacetylenoid compound, its preparation method, and its applications. The preparation method includes the following steps: (1) under a CO2 atmosphere, CO2 and a reducing agent react in an organic solvent to obtain a mixed solution; (2) adding a bifunctional terminal alkyne monomer, a bifunctional aryl iodine monomer, a catalyst, and a base to the mixed solution obtained in step (1) to carry out a multi-component polymerization reaction to obtain the polyacetylenoid compound. The preparation method of this invention has mild conditions, the monomers are simple and readily available, and the polymer yield is high. The polyacetylenoid compound obtained by this invention has good solubility, thermal stability, processing performance, and fluorescence performance, and has potential applications in the field of metal ion detection.

Description

Technical Field

[0001] This invention relates to the fields of polymer chemistry and materials science, specifically to a polyacetylenoid compound, its preparation method, and its applications. Background Technology

[0002] Carbon dioxide is a common gas in the atmosphere. With increasingly frequent human production and daily life activities and accelerated industrialization, carbon dioxide emissions are constantly increasing, leading to a growing severity of global climate change. However, carbon dioxide, as an abundant, inexpensive, non-toxic, and renewable C1 resource, also holds significant value in organic synthesis. Converting carbon dioxide into high-value-added fuels or materials, especially polymers, has become a research hotspot in recent years. Vigorously developing carbon dioxide-involved polymerization reactions can not only reduce greenhouse gas emissions but also generate polymers with unique properties, such as good thermal properties and biodegradability. Due to these unique properties, they have potential applications in biomedicine, packaging materials, and the automotive industry. Research on carbon dioxide polymerization reactions aligns with the concepts of green chemistry and sustainable development, contributing to my country's goals of carbon neutrality and carbon peaking, and promoting the chemical industry towards a more environmentally friendly and sustainable direction.

[0003] Over the past decades, the chemical applications of carbon dioxide have become diversified and efficient. Now, carbon dioxide can not only be converted into clean energy but also used to manufacture various high-value-added industrial products. Furthermore, various carbon dioxide-based polymerization technologies have been developed for the production of high-demand polymers such as polycarbonate, polyurethane, and polyurea. Some carbon dioxide polymerization technologies, after years of optimization, can efficiently synthesize high-molecular-weight carbon dioxide-based polymers. Nevertheless, these technologies still face challenges, such as the high cost, complex structure, and difficulty in preparing the metal catalysts used; the need for high-pressure conditions in polymerization processes; and a limited range of monomers available for polymerization, lacking innovation. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a method for preparing polyacetylacetonate compounds. This method can be carried out under normal pressure CO2 environment, and the reaction is simple and easy to operate.

[0005] Alkynes are important polymerizing monomers, possessing more diverse chemical properties compared to olefin monomers. Typically, polymers polymerized from alkyne monomers contain unsaturated chemical bonds, which endow the polymers with unique optoelectronic properties. The goal of this invention is to combine carbon dioxide with alkyne monomers to develop a novel, efficient, and mild polymerization reaction. This reaction can be carried out in a normal-pressure carbon dioxide environment, and through carefully designed monomer synthesis, a series of innovative functional polymers will be synthesized, providing new ideas and possibilities for the chemical conversion of carbon dioxide.

[0006] Another object of the present invention is to provide a polyacetylenoid compound prepared by the above method, which has good solubility, thermal stability, processability and fluorescence properties.

[0007] Another object of the present invention is to provide the application of the above-mentioned polyacetylenoid compound in the detection of metal ions.

[0008] The objective of this invention is achieved through the following technical solution:

[0009] This invention provides a method for preparing polyacetylenes ketone compounds, comprising the following steps:

[0010] (1) Under a CO2 atmosphere, CO2 and a reducing agent react in an organic solvent to obtain a mixed solution;

[0011] (2) Add the bifunctional terminal alkyne monomer, the bifunctional aryl iodine monomer, the catalyst and the base to the mixed solution obtained in step (1) to carry out a multi-component polymerization reaction to obtain polyacetylacetonate compounds;

[0012] The general structural formula of the difunctional terminal alkyne monomer is shown in formula (II):

[0013]

[0014] The general structural formula of the bifunctional aryl iodine monomer is shown in formula (Ⅲ):

[0015] I-R2-I (Ⅲ);

[0016] The general structural formula of the polyacetylenes is shown in formula (Ⅰ);

[0017]

[0018] In formulas (I) to (III), n is an integer from 2 to 200, R1 is an organic group, and R2 is an organic group with an aryl terminal.

[0019] Preferably, in formulas (I) to (III), R1 is selected from any one of the following chemical structural formulas 1 to 30 or 33 to 36; R2 is selected from any one of the following structural formulas 12 to 32;

[0020]

[0021]

[0022] Where m, n, k, i, and j are each an independent integer from 1 to 20; X is each independently selected from NR. 3 PR 4 O, S or Si(R) 5 )2, R 3 R 4 R 5 Each can be represented independently as -H or -CH3, with * indicating the substitution position.

[0023] Preferably, the reducing agent in step (1) is one or more of diethylsilane, phenylsilane, triphenylsilane, triethoxysilane, diphenylmethylsilane, dimethylphenylsilane, tetramethyldisiloxane and polymethylsiloxane;

[0024] Further preferably, the reducing agent is phenylsilane.

[0025] Preferably, the concentration of the reducing agent in step (1) in the organic solvent is 0.025–16 mol / L;

[0026] Preferably, the amount of reducing agent used in step (1) is 50-800 mol% of the difunctional terminal alkyne monomer.

[0027] Preferably, the CO2 atmosphere in step (1) is at atmospheric pressure; the molar amount of CO2 is greater than that of the reducing agent.

[0028] Preferably, the organic solvent in step (1) is one or more of tetrahydrofuran, dichloromethane, chloroform, toluene, 1,4-dioxane, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide. Considering the influence of the solvent on the polymerization reaction, it is further preferred that the organic solvent is N-methylpyrrolidone. In this case, the obtained polyacetylacetonate compound has better solubility, higher yield and molecular weight, and is easier to apply in the next step.

[0029] Preferably, the reaction temperature in step (1) is 20–220°C;

[0030] More preferably, the reaction temperature is 50–140°C.

[0031] Preferably, the reaction time in step (1) is 2 to 72 hours.

[0032] More preferably, the reaction time is 4 to 24 hours.

[0033] Preferably, the bifunctional terminal alkyne monomer, bifunctional aryl iodine monomer, catalyst, and base described in step (2) are dissolved in an organic solvent and added to the mixed solution obtained in step (1). The organic solvent is one or more of tetrahydrofuran, dichloromethane, chloroform, toluene, 1,4-dioxane, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; more preferably, the organic solvent is N-methylpyrrolidone.

[0034] Preferably, the concentration of the difunctional terminal alkyne monomer in step (2) in the reaction system is 0.05–2 mol / L;

[0035] Preferably, the molar ratio of the difunctional terminal alkyne monomer and the difunctional aryl iodide monomer in step (2) is (0.5-1.8):1;

[0036] Preferably, the polymerization reaction in step (2) takes 2 to 72 hours;

[0037] More preferably, the polymerization reaction takes 4 to 24 hours.

[0038] Preferably, the polymerization reaction in step (2) is carried out at a temperature of 30 to 200°C.

[0039] More preferably, the polymerization reaction temperature is 50–140°C.

[0040] Preferably, the catalyst in step (2) is a palladium catalyst.

[0041] Preferably, the catalyst in step (2) is one or more of palladium acetate, palladium chloride, tetra(triphenylphosphine) palladium, bis(triphenylphosphine) palladium dichloride, bis(tricyclohexylphosphine) palladium dichloride, bis(diphenylphosphine) ferrocene palladium dichloride, and tri(dibenzylacetone) palladium.

[0042] More preferably, the catalyst is bis(tricyclohexylphosphine)palladium dichloride.

[0043] Preferably, the amount of catalyst used in step (2) is 5-60 mol of the difunctional terminal alkyne monomer.

[0044] Preferably, the alkali mentioned in step (2) is one or more of cesium carbonate, sodium carbonate, potassium carbonate, potassium phosphate, triethylamine, triethylenediamine, N,N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, ammonia, triethanolamine, monoethanolamine, potassium tert-butoxide, cesium fluoride, 1,8-diazabicycloundec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and tetramethylammonium hydroxide;

[0045] More preferably, the base is triethylamine.

[0046] Preferably, the amount of alkali used in step (2) is 50-800 mol% of the difunctional terminal alkyne monomer.

[0047] Preferably, after the polymerization reaction in step (2) is completed, the product is dissolved in an organic solvent and then added to methanol, n-hexane or diethyl ether for precipitation. The precipitate is collected and dried to constant weight to obtain polyacetylacetonate compounds.

[0048] The present invention also provides a polyacetylenoid compound prepared by the above-described preparation method.

[0049] The polyacetylacetonate compounds of this invention have good thermal stability, solubility and excellent processability, and have good application prospects in the field of metal ion detection.

[0050] The present invention also provides the application of the above-mentioned polyacetylacetonate compounds in the detection of metal ions.

[0051] Preferably, the R1 of the polyacetylacetonate compound has structural formula 25; the metal ion is a trivalent ruthenium ion.

[0052] Compared with the prior art, the present invention has the following advantages:

[0053] (1) The preparation method of the present invention can be carried out under normal pressure CO2 atmosphere, and participates in polymerization as a carbonyl source, without the need to control the carbon dioxide feed ratio. Therefore, it is innovative and of great significance.

[0054] (2) The preparation method of the present invention is simple to operate, the reaction raw materials and catalysts are readily available and can be purchased directly or prepared through simple reactions; the reaction conditions are mild, the process is simple, energy is saved, and the polymer yield is high; CO2 is widely available and low in cost.

[0055] (3) The preparation method of the present invention has good functional group tolerance and can introduce a variety of functional groups.

[0056] (4) The functionalized polyacetylenes obtained by this invention have good solubility, thermal stability, processability and fluorescence properties, and have potential application prospects in the field of metal ion detection. Attached Figure Description

[0057] Figure 1 Comparison of the proton NMR spectra of the polyacetylacetonate compounds and their corresponding monomers prepared in deuterated chloroform in Example 1 of this invention (* represents solvent peaks).

[0058] Figure 2 Comparison of carbon NMR spectra of the polyacetylenes prepared in Example 1 of this invention and their corresponding monomers in deuterated chloroform (* represents solvent peaks).

[0059] Figure 3 The infrared absorption spectra of the polyacetylenes and their corresponding monomers prepared in Example 1 of this invention are shown.

[0060] Figure 4 The thermogravimetric curves of the polyacetylenes prepared in Example 1 of this invention are shown.

[0061] Figure 5 The polyacetylacetonate compound prepared in Example 3 of this invention (concentration of 10 based on repeating units) -5 Selective detection of metal ions in a 90% water-volume THF / H2O mixed solution (mol / L), where I0 is the fluorescence intensity of the solution without added metal ions, and I is the fluorescence intensity of the solution with added metal ions (10 mol / L). -5 The fluorescence intensity after (mol / L) was measured, and the excitation wavelength was 350 nm. Detailed Implementation

[0062] The present invention will now be described in detail with reference to the embodiments, but the scope of protection of the present invention is not limited to the following embodiments.

[0063] Example 1

[0064] A polyacetylacetonate compound, the structural formula of which is shown in P1:

[0065]

[0066] The polyacetylacetonate compounds are prepared by polymerization of CO2, difunctional terminal alkynes, and difunctional aryl iodides, as shown in equation (I):

[0067]

[0068] CO2 can be purchased from the market, and in this embodiment it was purchased from Guangzhou Shengying Chemical Co., Ltd. The synthesis methods of monomers M1 and N1 can be referred to the synthesis methods in the literature (Polymer Chemistry 2018,9(34),4404-4412).

[0069] The preparation steps of the polyacetylenes are as follows:

[0070] A magnetic ball was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A CO2-filled balloon was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) containing phenylsilane (259.7 mg, 2.4 mmol) was injected. The reaction was carried out at 60 °C for 6 h. Then, M1 (88.0 mg, 0.3 mmol), N1 (156.7 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (44.3 mg, 0.06 mmol), and triethylamine (182.1 mg, 1.8 mmol) were dissolved in 1 mL of NMP and injected into the reaction system. The reaction was carried out at 60 °C for 7 h. The mixture was then cooled to room temperature, and 3 mL of dichloromethane (DCM) was added to dissolve it. The resulting polymer solution was filtered through a cotton sieve and added dropwise to methanol stirred at 700 rpm. The mixture was then allowed to stand, filtered, and dried to constant weight to obtain polyacetylacetonate compound P1.

[0071] Analysis revealed that the final product, polyacetylenoid compound P1, had a yield of 99%, a weight-average molecular weight of 11800 g / mol, and a molecular weight distribution of 1.88. A comparison of the NMR spectra of this polyacetylenoid compound and its corresponding monomer (* represents solvent peaks) is shown below. Figure 1 , Figure 2 . Figure 1 In the structure, chemical shifts of 4.03 ppm, 1.87 ppm, and 1.54 ppm correspond to the characteristic peaks of the methylene hydrogen atom, respectively. Figure 2 In the analysis, the characteristic peak of the newly formed carbonyl carbon in the polymer is located at a chemical shift of 177.70 ppm, the characteristic peaks of the carbon atoms on the endoyne are located at chemical shifts of 94.10 ppm and 87.47 ppm, and the characteristic peaks of the carbon atoms on the methylene group in the structure are located at chemical shifts of 68.14 ppm, 28.99 ppm and 25.46 ppm, respectively. Therefore, the polymer can be identified as a polyacetylenoid compound. Figure 3 The infrared absorption spectra of the polyacetylenoid compounds and their corresponding monomers prepared in this embodiment are shown. The changes in the infrared absorption peaks of the acetylenic and carbonyl groups further confirm the successful conduction of the reaction. Figure 4 The thermogravimetric curve of the polyacetylenoid compound prepared for this invention shows that the temperature at which 5% weight loss occurs is 356°C, indicating good thermal stability. Furthermore, this polyacetylenoid compound is readily soluble in organic solvents such as dichloromethane, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide at room temperature, demonstrating good solubility and processability.

[0072] Example 2

[0073] A polyacetylacetonate compound, the structural formula of which is shown on P2:

[0074]

[0075] The polyacetylacetonate compounds are prepared by polymerization of CO2, difunctional terminal alkynes, and difunctional aryl iodides, as shown in equation (II):

[0076]

[0077] CO2 can be purchased from the market; in this embodiment, it was purchased from Guangzhou Shengying Chemical Co., Ltd. The synthesis method of monomer M1 is the same as in Example 1. The synthesis method of monomer N2 can be referred to the synthesis method in the literature (Polymer Chemistry 2018, 9(34), 4404-4412).

[0078] The preparation steps of the polyacetylenes are as follows:

[0079] A magnetic ball was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A CO2-filled balloon was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) containing phenylsilane (259.7 mg, 2.4 mmol) was injected. The reaction was carried out at 60 °C for 6 h. Then, M1 (88.0 mg, 0.3 mmol), N2 (156.7 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (44.3 mg, 0.06 mmol), and triethylamine (182.1 mg, 1.8 mmol) were dissolved in 1 mL of NMP and injected into the reaction system. The reaction was carried out at 60 °C for 7 h. The mixture was then cooled to room temperature, and 3 mL of dichloromethane (DCM) was added to dissolve it. The resulting polymer solution was filtered through a cotton sieve and added dropwise to methanol stirred at 700 rpm. The mixture was then allowed to stand, filtered, and dried to constant weight to obtain polyacetylenic ketone compound P2.

[0080] Analysis revealed that the final product, polyacetylenoid compound P2, had a yield of 97%, a weight-average molecular weight of 9800 g / mol, and a molecular weight distribution of 1.68. Furthermore, this polyacetylenoid compound is readily soluble in organic solvents such as dichloromethane, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide at room temperature, indicating good solubility and processability.

[0081] Example 3

[0082] A polyacetylacetonate compound, the structural formula of which is shown on page 3:

[0083]

[0084] The polyacetylacetonate compounds are prepared by polymerization of CO2, difunctional terminal alkynes, and difunctional aryl iodides, as shown in equation (III):

[0085]

[0086] CO2 can be purchased from the market; in this embodiment, it was purchased from Guangzhou Shengying Chemical Co., Ltd. The synthesis method of monomer N1 is the same as in Example 1, and M2 was purchased from Aode Technology Co., Ltd.

[0087] The preparation steps of the polyacetylenes are as follows:

[0088] A magnetic ball was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A CO2-filled balloon was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) containing phenylsilane (259.7 mg, 2.4 mmol) was injected. The reaction was carried out at 60 °C for 6 h. Then, M2 (114.1 mg, 0.3 mmol), N1 (156.7 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (44.3 mg, 0.06 mmol), and triethylamine (182.1 mg, 1.8 mmol) were dissolved in 1 mL of NMP and injected into the reaction system. The reaction was carried out at 60 °C for 7 h. The mixture was then cooled to room temperature, and 3 mL of dichloromethane (DCM) was added to dissolve it. The resulting polymer solution was filtered through a cotton sieve and added dropwise to methanol stirred at 700 rpm. The mixture was then allowed to stand, filtered, and dried to constant weight to obtain polyacetylacetonate compound P3.

[0089] Analysis revealed that the final product, polyacetylenoid compound P3, had a yield of 87%, a weight-average molecular weight of 7500 g / mol, and a molecular weight distribution of 1.42. Furthermore, this polyacetylenoid compound is readily soluble in organic solvents such as dichloromethane, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide at room temperature, indicating good solubility and processability.

[0090] Because its structure contains tetraphenylvinyl groups, it can emit excellent fluorescence in its aggregated state in aqueous solutions, such as Figure 5 As shown, when 13 metal ions are added, only trivalent ruthenium ions undergo fluorescence quenching, thus enabling the specific detection of metal ions.

[0091] Example 4

[0092] A polyacetylacetonate compound, the structural formula of which is shown on page 4:

[0093]

[0094] The polyacetylacetonate compounds are prepared by polymerization of CO2, difunctional terminal alkynes, and difunctional aryl iodides, as shown in equation (iv):

[0095]

[0096] CO2 can be purchased from the market; in this embodiment, it was purchased from Guangzhou Shengying Chemical Co., Ltd. The synthesis method of monomer N2 is the same as in Example 2, and M2 was purchased from Aode Technology Co., Ltd.

[0097] The preparation steps of the polyacetylenes are as follows:

[0098] A magnetic ball was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A CO2-filled balloon was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) containing phenylsilane (259.7 mg, 2.4 mmol) was injected. The reaction was carried out at 60 °C for 6 h. Then, M2 (114.1 mg, 0.3 mmol), N2 (156.7 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (44.3 mg, 0.06 mmol), and triethylamine (182.1 mg, 1.8 mmol) were dissolved in 1 mL of NMP and injected into the reaction system. The reaction was carried out at 60 °C for 7 h. The mixture was then cooled to room temperature, and 3 mL of dichloromethane (DCM) was added to dissolve it. The resulting polymer solution was filtered through a cotton sieve and added dropwise to methanol stirred at 700 rpm. The mixture was then allowed to stand, filtered, and dried to constant weight to obtain the polyacetylenic ketone compound P4.

[0099] Analysis revealed that the final product, polyacetylenoid compound P4, had a yield of 91%, a weight-average molecular weight of 11800 g / mol, and a molecular weight distribution of 1.82. Furthermore, this polyacetylenoid compound is readily soluble in organic solvents such as dichloromethane, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide at room temperature, indicating good solubility and processability.

[0100] Comparative Example 1

[0101] Based on Example 1, the aryl iodine was replaced with an alkyl iodine for the reaction, and the steps are as follows:

[0102] CO2 can be purchased from the market; in this embodiment, it was purchased from Guangzhou Shengying Chemical Co., Ltd.; the monomer 1,6-diiodohexane was purchased from Anaiji Chemical.

[0103] A magnetic stir bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A CO2-filled balloon was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) containing dissolved phenylsilane (259.7 mg, 2.4 mmol) was injected. The reaction was carried out at 60 °C for 6 h. Then, M1 (88.0 mg, 0.3 mmol), 1,6-diiodohexane (101.39 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (44.3 mg, 0.06 mmol), and triethylamine (182.1 mg, 1.8 mmol) were dissolved in 1 mL of NMP and injected into the reaction system. The reaction was carried out at 60 °C for 7 h, and then cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the polymer. The resulting polymer solution was filtered through a cotton swab and added dropwise to methanol stirred at 700 rpm. The mixture was then allowed to stand, filtered, and dried to constant weight. The polymer yield was only 24%, indicating that alkyl iodine is not suitable for this polymerization reaction.

[0104] Comparative Example 2

[0105] Based on Example 1, the reaction is carried out without adding a reducing agent, and the steps are as follows:

[0106] CO2 can be purchased from the market; in this embodiment, it was purchased from Guangzhou Shengying Chemical Co., Ltd. The synthesis methods of monomers M1 and N1 are the same as in Example 1.

[0107] A magnetic stir bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A CO2-filled balloon was then inserted. M1 (88.0 mg, 0.3 mmol), N1 (156.7 mg, 0.3 mmol), bis(tricyclohexylphosphine)palladium dichloride (44.3 mg, 0.06 mmol), and triethylamine (182.1 mg, 1.8 mmol) were dissolved in 1.5 mL of NMP and injected into the reaction system. The reaction was carried out at 60 °C for 7 h, then cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the polymer. The resulting polymer solution was filtered through a cotton swab and added dropwise to methanol stirred at 700 rpm. The mixture was then allowed to stand, filtered, and dried to constant weight. The polymer yield was only 8%, indicating that the reducing agent plays an indispensable role in this polymerization reaction.

Claims

1. A method for preparing a polyacetylenoid compound, characterized in that, Includes the following steps: (1) Under a CO2 atmosphere, CO2 and a reducing agent react in an organic solvent to obtain a mixed solution; (2) Add the bifunctional terminal alkyne monomer, the bifunctional aryl iodine monomer, the catalyst and the base to the mixed solution obtained in step (1) to carry out a multi-component polymerization reaction to obtain polyacetylacetonate compounds; The general structural formula of the difunctional terminal alkyne monomer is shown in formula (II): The general structural formula of the bifunctional aryl iodine monomer is shown in formula (Ⅲ): I-R2-I (Ⅲ); The general structural formula of the polyacetylenes is shown in formula (Ⅰ); In formulas (I) to (III), n is an integer from 2 to 200, R1 is an organic group, and R2 is an organic group with an aryl terminal. In formulas (I) to (III), R1 is selected from any one of the following chemical structural formulas 1 to 30 or 33 to 36; R2 is selected from any one of the following structural formulas 12 to 30. Where m, n, k, i, and j are each an independent integer from 1 to 20; X is each independently selected from NR. 3 PR 4 O, S or Si(R) 5 )2, R 3 R 4 R 5 Each can be represented independently as -H or -CH3, with * indicating the substitution position; The reducing agent mentioned in step (1) is one or more of diethylsilane, phenylsilane, triphenylsilane, triethoxysilane, diphenylmethylsilane, dimethylphenylsilane, tetramethyldisiloxane and polymethylsiloxane; The concentration of the reducing agent in the organic solvent in step (1) is 0.025–16 mol / L; the amount of the reducing agent is 50–800 mol% of the difunctional terminal alkyne monomer; and the CO2 atmosphere is at atmospheric pressure. The organic solvent mentioned in step (1) is one or more of tetrahydrofuran, dichloromethane, chloroform, toluene, 1,4-dioxane, acetonitrile, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide and N,N-dimethylacetamide; The reaction temperature in step (1) is 20–220 °C; The reaction time described in step (1) is 2 to 72 hours.

2. The method for preparing polyacetylenes according to claim 1, characterized in that, The concentration of the difunctional terminal alkyne monomer in the reaction system in step (2) is 0.05–2 mol / L; The molar ratio of the difunctional terminal alkyne monomer and the difunctional aryl iodide monomer in step (2) is (0.5-1.8):1; The polymerization reaction in step (2) takes 2 to 72 hours. The polymerization reaction in step (2) is carried out at a temperature of 30 to 200°C.

3. The method for preparing polyacetylenoid compounds according to claim 1, characterized in that, The catalyst mentioned in step (2) is one or more of palladium acetate, palladium chloride, tetra(triphenylphosphine) palladium, bis(triphenylphosphine) palladium dichloride, bis(tricyclohexylphosphine) palladium dichloride, bis(diphenylphosphine) ferrocene palladium dichloride, and tri(dibenzylideneacetone) palladium; The amount of catalyst used in step (2) is 5-60 mol of the difunctional terminal alkyne monomer.

4. The method for preparing polyacetylenoid compounds according to claim 1, characterized in that, The alkali mentioned in step (2) is one or more of the following: cesium carbonate, sodium carbonate, potassium carbonate, potassium phosphate, triethylamine, triethylenediamine, N,N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, ammonia, triethanolamine, monoethanolamine, potassium tert-butoxide, cesium fluoride, 1,8-diazabicycloundec-7-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and tetramethylammonium hydroxide; The amount of alkali used in step (2) is 50-800 mol of the difunctional terminal alkyne monomer.

5. The method for preparing polyacetylenoid compounds according to claim 1, characterized in that, After the polymerization reaction in step (2) is completed, the product is dissolved in an organic solvent and then added to methanol, n-hexane or diethyl ether for precipitation. The precipitate is collected and dried to constant weight to obtain polyacetylacetonate compounds.

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