Polyacetylenic ketone compound as well as preparation method and application thereof

Abstract

The invention discloses a polyacetylenic ketone compound and a preparation method and application thereof, and the preparation method comprises the following steps: (1) in a CO2 atmosphere, CO2 and a reducing agent react in an organic solvent to obtain a mixed solution; and (2) adding a bifunctional terminal alkyne monomer, a bifunctional aryl iodine monomer, a catalyst and alkali into the mixed solution obtained in the step (1), and carrying out multi-component polymerization reaction to obtain the polyacetylenic ketone compound. The preparation method is mild in condition, the polymerization monomer is simple and easy to obtain, and the polymer yield is high. The polyacetylenic ketone compound obtained by the invention has better solubility, thermal stability, processability and fluorescence property, and has potential application in the field of metal ion detection.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer chemistry and materials science, and in particular to a polyacetylenic ketone compound and a preparation method and application thereof. Background Art

[0002] Carbon dioxide is a common gas in the atmosphere. With the increasing frequency of human production and life activities and the acceleration of the industrialization process, carbon dioxide emissions are also increasing, leading to increasingly serious global climate change problems. But at the same time, as an abundant, cheap, non-toxic and renewable C1 resource, carbon dioxide has important value in organic synthesis. Converting carbon dioxide into high-value-added fuels or materials, especially polymer materials, has been one of the research hotspots in recent years. Vigorously developing polymerization reactions involving carbon dioxide can not only reduce greenhouse gas emissions, but also generate polymers with special properties. These polymers have good thermal properties and biodegradability. Due to their unique properties, they have potential application value in biomedicine, packaging materials, automotive industry and other fields. The research on carbon dioxide polymerization reaction is in line with the concept of green chemistry and sustainable development, helping to achieve my country's carbon neutrality and carbon peak goals, and promoting the chemical industry to develop in a more environmentally friendly and sustainable direction.

[0003] After decades of development, the chemical application of carbon dioxide has become diversified and efficient. Now, carbon dioxide can not only be converted into clean energy, but also produce a variety of high value-added industrial products. In addition, a variety of carbon dioxide-related polymerization reaction technologies have been developed for the production of high-demand polymer materials such as polycarbonate, polyurethane, polyurea, etc. After years of optimization, some carbon dioxide polymerization reaction technologies have been able to efficiently synthesize high molecular weight carbon dioxide-based polymers. Despite this, these technologies still face some challenges, such as the high cost, complex structure and difficulty in preparation of the metal catalysts used; the polymerization process usually needs to be carried out under high pressure conditions; and the limited types of monomers that can be used for polymerization lack innovation. Summary of the invention

[0004] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing a polyacetylene ketone compound, which can be carried out under a normal pressure CO2 environment and has a simple reaction and is easy to operate.

[0005] Alkynes are an important type of polymerization monomer that possesses more diverse chemical properties than olefin monomers. Typically, polymers formed from alkyne monomers contain unsaturated chemical bonds that give the polymer unique optoelectronic properties. The goal of this invention is to combine carbon dioxide with alkyne monomers to develop a new, efficient, and mild polymerization reaction. This reaction can be carried out in a normal pressure carbon dioxide environment, and a series of innovative functional polymers synthesized from carefully designed monomers will provide new ideas and possibilities for the chemical transformation of carbon dioxide.

[0006] Another object of the present invention is to provide a polyalkynyl ketone compound prepared by the above method, wherein the polyalkynyl ketone compound has good solubility, thermal stability, processing performance and fluorescence performance.

[0007] Another object of the present invention is to provide an application of the above-mentioned polyacetylenic ketone compound in metal ion detection.

[0008] The purpose of the present invention is achieved through the following technical solutions:

[0009] The present invention provides a method for preparing a polyacetylene ketone compound, 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) adding a bifunctional terminal acetylene monomer, a bifunctional aryl iodide monomer, a catalyst and a base to the mixed solution obtained in step (1) to carry out a multi-component polymerization reaction to obtain a polyacetylene ketone compound;

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

[0013]

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

[0015] I-R2-I (III);

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

[0017]

[0018] In formulae (I) to (III), n is an integer of 2 to 200, R1 is an organic group, and R2 is an organic group having an aromatic group at the end.

[0019] Preferably, in the formulas (I) to (III), R1 is selected from any one of the following chemical 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] wherein m, n, k, i, and j are each independently an integer from 1 to 20; and X is each independently selected from NR 3 , PR 4 , O, S or Si(R 5 )2,R 3 , R 4 , R 5 Each is independently -H or -CH3, and * indicates a 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] More preferably, the reducing agent is phenylsilane.

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

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

[0027] Preferably, the CO2 atmosphere in step (1) is at normal 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 polyacetylenic ketone compound has good solubility, high yield and molecular weight, which is convenient for the next step application.

[0029] Preferably, the reaction temperature in step (1) is 20 to 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 acetylene monomer, bifunctional aryl iodide monomer, catalyst and base 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 bifunctional terminal acetylenic monomer in the reaction system in step (2) is 0.05 to 2 mol / L;

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

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

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

[0038] Preferably, the polymerization reaction temperature in step (2) is 30-200°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, tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, bis(tricyclohexylphosphine)palladium dichloride, bis(diphenylphosphino)ferrocenepalladium dichloride and tris(dibenzylideneacetone)dipalladium;

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

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

[0044] Preferably, the base 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 water, 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 the base used in step (2) is 50 to 800 mol % of the difunctional terminal acetylene 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 a polyacetylene ketone compound.

[0048] The present invention also provides a polyacetylenic ketone compound, which is prepared by the above-mentioned preparation method.

[0049] The polyacetylenic ketone compound of the present invention has good thermal stability, solubility and excellent processability, and has good application prospects in the field of metal ion detection.

[0050] The present invention also provides the use of the polyacetylenic ketone compound in metal ion detection.

[0051] Preferably, R1 of the polyacetylenic ketone compound is of structural formula 25; and 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 a normal pressure CO2 atmosphere, and can participate in the polymerization as a carbonyl source without controlling the carbon dioxide feed ratio. Therefore, the preparation method of the present invention is innovative and extremely important.

[0054] (2) The preparation method of the present invention is simple to operate. The reaction raw materials and catalysts are easily 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. The CO2 source is wide and the cost is low.

[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 polyacetylenic ketone compounds prepared by the present invention have good solubility, thermal stability, processability and fluorescence properties, and have potential application prospects in the fields of metal ion detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is a comparison chart of the H NMR spectra of the polyacetylenic ketone compound and its corresponding monomer prepared in Example 1 of the present invention in deuterated chloroform (* represents the solvent peak).

[0058] Figure 2 This is a comparison chart of the carbon NMR spectra of the polyacetylenic ketone compounds and their corresponding monomers prepared in Example 1 of the present invention in deuterated chloroform (* represents the solvent peak).

[0059] Figure 3 This is an infrared absorption spectrum of the polyacetylenic ketone compound and its corresponding monomer prepared in Example 1 of the present invention.

[0060] Figure 4 This is the thermogravimetric curve of the polyacetylenic ketone compound prepared in Example 1 of the present invention.

[0061] Figure 5 The polyacetin ketone compound (concentration of 10 in terms of repeating units) prepared in Example 3 of the present invention -5 mol / L) in a THF / H2O mixed solution with a water content of 90% by volume, where I0 is the fluorescence intensity of the solution without metal ions, and I is the fluorescence intensity of the solution with metal ions (10 -5 mol / L), and the excitation wavelength was 350 nm. DETAILED DESCRIPTION

[0062] The present invention is described in detail below in conjunction with the embodiments, but the protection scope of the present invention is not limited to the following embodiments.

[0063] Example 1

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

[0065]

[0066] The polyacetylenic ketone compound is prepared by polymerization reaction of CO2, bifunctional terminal alkyne and bifunctional aryl iodide, and the reaction equation is as follows:

[0067]

[0068] Among them, CO2 can be purchased from the market, and in this embodiment, it is purchased from Guangzhou Shengying Chemical Co., Ltd.; the synthesis method of monomers M1 and N1 can be synthesized by referring to the synthesis method of the literature (Polymer Chemistry 2018, 9(34), 4404-4412).

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

[0070] A magnetic bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A balloon filled with CO2 was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) dissolved with phenylsilane (259.7 mg, 2.4 mmol) was injected. The tube was reacted at 60° C. for 6 h. Then, 1 mL of NMP was used to dissolve 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), and the mixture was injected into the reaction system. The tube was reacted at 60° C. for 7 h, and then cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the mixture. The obtained polymer solution was passed through a cotton filter and added dropwise into methanol stirred at 700 rpm, and then allowed to stand, filtered, and dried to constant weight to obtain a polyacetylene ketone compound P1.

[0071] After analysis, the yield of the final product polyacetylene ketone compound P1 was 99%, the weight average molecular weight was 11800 g / mol, and the molecular weight distribution was 1.88. The NMR spectrum comparison of the polyacetylene ketone compound and its corresponding monomer (* represents the solvent peak) is shown in Figure 1 , Figure 2 . Figure 1 In the , the chemical shifts at 4.03ppm, 1.87ppm, and 1.54ppm correspond to the characteristic peaks of the methylene hydrogen atoms in the structure; Figure 2 In the results, the chemical shift of 177.70 ppm corresponds to the characteristic peak of the newly generated carbonyl carbon of the polymer, the chemical shifts of 94.10 ppm and 87.47 ppm correspond to the characteristic peaks of the carbon atoms on the internal alkyne, and the chemical shifts of 68.14 ppm, 28.99 ppm and 25.46 ppm correspond to the characteristic peaks of the carbon atoms on the methylene group in the structure, respectively. Therefore, it can be determined that the polymer is a polyacetylene ketone compound. Figure 3 The infrared absorption spectra of the polyacetylenic ketone compounds and their corresponding monomers prepared in this example further confirm the successful progress of the reaction through the changes in the infrared absorption peaks of the acetylenic group and the carbonyl group. Figure 4 The thermogravimetric curve of the polyacetylene ketone compound prepared by the present invention shows that the temperature at which the weight loss is 5% is 356°C, indicating good thermal stability. In addition, the polyacetylene ketone compound is easily 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.

[0072] Example 2

[0073] A polyacetylene ketone compound, the structural formula of which is shown in P2:

[0074]

[0075] The polyacetylenic ketone compound is prepared by polymerization reaction of CO2, bifunctional terminal alkyne and bifunctional aryl iodide, and the reaction equation is as follows:

[0076]

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

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

[0079] A magnetic bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A balloon filled with CO2 was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) dissolved with phenylsilane (259.7 mg, 2.4 mmol) was injected. The tube was reacted at 60° C. for 6 h. Then, 1 mL of NMP was used to dissolve 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), and the mixture was injected into the reaction system. The tube was reacted at 60° C. for 7 h, and then cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the mixture. The obtained polymer solution was passed through a cotton filter and added dropwise into methanol stirred at 700 rpm, and then allowed to stand, filtered, and dried to constant weight to obtain a polyalkynyl ketone compound P2.

[0080] After determination and analysis, the yield of the final product polyacetylene ketone compound P2 is 97%, the weight average molecular weight is 9800 g / mol, and the molecular weight distribution is 1.68. In addition, the polyacetylene ketone compound is easily 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 polyacetylene ketone compound, the structural formula of which is shown in P3:

[0083]

[0084] The polyacetylenic ketone compound is prepared by polymerization reaction of CO2, bifunctional terminal alkyne and bifunctional aryl iodide, and the reaction equation is as follows:

[0085]

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

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

[0088] A magnetic bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A balloon filled with CO2 was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) dissolved with phenylsilane (259.7 mg, 2.4 mmol) was injected. The reaction was carried out at 60° C. for 6 h. Then, 1 mL of NMP was used to dissolve 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), and the mixture was injected into the reaction system. The reaction was carried out at 60° C. for 7 h, and then the mixture was cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the mixture. The obtained polymer solution was passed through a cotton filter and added dropwise into methanol stirred at 700 rpm, and then allowed to stand, filtered, and dried to constant weight to obtain a polyacetylenic ketone compound P3.

[0089] The final product polyacetylene ketone compound P3 has a yield of 87%, a weight average molecular weight of 7500 g / mol, and a molecular weight distribution of 1.42. In addition, the polyacetylene ketone compound is easily 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 of the tetraphenylethylene group in its structure, the aggregated state can emit excellent fluorescence in aqueous solution, such as Figure 5 As shown, when 13 metal ions were added, only trivalent ruthenium ions underwent fluorescence quenching, thus achieving specific detection of metal ions.

[0091] Example 4

[0092] A polyacetylene ketone compound, the structural formula of which is shown in P4:

[0093]

[0094] The polyacetylenic ketone compound is prepared by polymerization reaction of CO2, bifunctional terminal alkyne and bifunctional aryl iodide, and the reaction equation is as shown in Formula (IV):

[0095]

[0096] Among them, CO2 can be purchased from the market, and 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 is purchased from Aode Technology Co., Ltd.

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

[0098] A magnetic bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A balloon filled with CO2 was inserted, and 0.5 mL of N-methylpyrrolidone (NMP) dissolved with phenylsilane (259.7 mg, 2.4 mmol) was injected. The tube was reacted at 60° C. for 6 h. Then, 1 mL of NMP was used to dissolve 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), and the mixture was injected into the reaction system. The tube was reacted at 60° C. for 7 h, and then cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the mixture. The obtained polymer solution was passed through a cotton filter and added dropwise into methanol stirred at 700 rpm, and then allowed to stand, filtered, and dried to constant weight to obtain polyacetylene ketone compound P4.

[0099] After determination and analysis, the yield of the final product polyacetylene ketone compound P4 is 91%, the weight average molecular weight is 11800 g / mol, and the molecular weight distribution is 1.82. In addition, the polyacetylene ketone compound is easily 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 iodide is replaced by an alkyl iodide to carry out the reaction, and the steps are as follows:

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

[0103] A magnetic bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A balloon filled with CO2 was inserted, and 0.5 mL N-methylpyrrolidone (NMP) containing phenylsilane (259.7 mg, 2.4 mmol) was injected. The tube was reacted at 60°C for 6 h. Then, 1 mL of NMP was used to dissolve 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), and injected into the reaction system. The tube was reacted at 60°C for 7 h, and then cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the polymer solution. The obtained polymer solution was added dropwise to methanol stirred at 700 rpm through a cotton filter, and then allowed to stand, filtered, and dried to constant weight. The obtained polymer yield was only 24%. This indicates that alkyl iodide is not suitable for this polymerization reaction.

[0104] Comparative Example 2

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

[0106] Among them, CO2 can be purchased from the market, and in this embodiment it is purchased from Guangzhou Shengying Chemical Co., Ltd.; the synthesis method of monomers M1 and N1 is the same as that in Example 1.

[0107] A magnetic bar was added to a dry 10 mL polymerization tube, and the tube was evacuated for 20 minutes. A balloon filled with CO2 was inserted, and 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 tube was reacted at 60°C for 7 hours, and then cooled to room temperature. 3 mL of dichloromethane (DCM) was added to dissolve the polymer solution. The obtained polymer solution was passed through a cotton filter and added dropwise to methanol stirred at 700 rpm, and then allowed to stand, filtered, and dried to constant weight. The obtained polymer yield was only 8%. This shows that the reducing agent plays an indispensable role in this polymerization reaction.

Claims

1. A method for preparing a polyacetylene ketone compound, characterized in that: The following steps are involved: (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 acetylene monomer, a bifunctional aryl iodide monomer, a catalyst and a base to the mixed solution obtained in step (1) to carry out a multi-component polymerization reaction to obtain a polyacetylene ketone compound; The general structural formula of the bifunctional terminal acetylenic monomer is shown in formula (II): The general structural formula of the bifunctional aromatic iodide monomer is shown in formula (III): l—R2-l(III); The general structural formula of the polyacetylene ketone compound is shown in formula (I); In formulae (I) to (III), n is an integer of 2 to 200, R1 is an organic group, and R2 is an organic group having an aromatic group at the end.

2. The method for preparing a polyalkynyl ketone compound according to claim 1, wherein In the 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; wherein m, n, k, i, and j are each independently an integer from 1 to 20; and X is each independently selected from NR 3 , PR 4 , O, S or Si(R 5 )2,R 3 , R 4 , R 5 Each is independently -H or -CH3, and * indicates a substitution position.

3. The method for preparing a polyalkynyl ketone compound according to claim 1, wherein The reducing agent in step (1) is one or more of diethylsilane, phenylsilane, triphenylsilane, triethoxysilane, diphenylmethylsilane, dimethylphenylsilane, tetramethyldisiloxane and polymethylsiloxane; The concentration of the reducing agent in step (1) in the organic solvent is 0.025 to 16 mol / L; The amount of the reducing agent used in step (1) is 50 to 800 mol% of the difunctional terminal acetylene monomer.

4. The method for preparing a polyalkynyl ketone compound according to claim 1, wherein The CO2 atmosphere in step (1) is at normal pressure; 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; The reaction temperature of step (1) is 20 to 220°C; The reaction time of step (1) is 2 to 72 hours.

5. The method for preparing a polyalkynyl ketone compound according to claim 1, wherein The concentration of the bifunctional terminal acetylenic monomer in the reaction system in step (2) is 0.05 to 2 mol / L; The molar ratio of the bifunctional terminal acetylenic monomer to the bifunctional aryl iodide monomer in step (2) is (0.5-1.8):1; The polymerization reaction time of step (2) is 2 to 72 hours; The temperature of the polymerization reaction in step (2) is 30-200°C.

6. The method for preparing the polyalkynyl ketone compound according to claim 1, characterized in that: The catalyst in step (2) is one or more of palladium acetate, palladium chloride, tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, bis(tricyclohexylphosphine)palladium dichloride, bis(diphenylphosphino)ferrocenepalladium dichloride and tris(dibenzylideneacetone)dipalladium; The amount of the catalyst used in step (2) is 5 to 60 mol% of the difunctional terminal acetylene monomer.

7. The method for preparing a polyalkynyl ketone compound according to claim 1, characterized in that: The base 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 water, 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 the base used in step (2) is 50 to 800 mol% of the difunctional terminal acetylene monomer.

8. The method for preparing a polyalkynyl ketone compound 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 a polyacetylene ketone compound.

9. A polyacetylenic ketone compound, characterized in that The compound is prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the polyalkynyl ketone compound according to claim 9 in metal ion detection.

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