Fused heterocyclic polymer, and preparation method therefor and use thereof

Abstract

The present application relates to the technical field of polymer material preparation, and in particular to a fused heterocyclic polymer, and a preparation method therefor and a use thereof. The fused heterocyclic polymer of the present application has a special structure, high thermal stability and excellent processability, and has good application prospects. The polymer exhibits bright fluorescence in both a solution state and an aggregated state, and can be used in optical materials. The fused heterocyclic polymer of the present application undergoes fluorescence quenching upon interacting with Ag+, and can qualitatively detect metal Ag+ ions.

Description

A fused heterocyclic polymer, its preparation method and application

[0001] Cross-references to related applications

[0002] This application claims priority to Chinese Patent Application No. 202510101404.8, filed on January 22, 2025, entitled "A Fused Heterocyclic Polymer and Its Preparation Method and Application", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application belongs to the field of polymer material preparation technology, specifically relating to a fused heterocyclic polymer, its preparation method and application. Background Technology

[0004] Carbon dioxide is a major greenhouse gas, and its excessive emissions contribute to global warming. Converting CO2 into useful chemicals, such as polycarbonates, polyurethanes, and fused heterocyclic polymers, can not only reduce atmospheric CO2 concentrations and mitigate the greenhouse effect but also achieve resource recycling. This conversion process embodies the concept of "carbon capture and utilization" (CCU). As an abundant, non-toxic, low-cost, and sustainable C1 feedstock, CO2 can be transformed into high-value-added chemicals through multi-component polymerization (MCP), which not only helps reduce environmental pollution but also promotes sustainable economic development. Therefore, finding better ways to utilize CO2 is of great significance. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this application is to overcome the above-mentioned technical problems, thereby providing a fused heterocyclic polymer, its preparation method and application.

[0006] Therefore, this application provides the following technical solution.

[0007] This application provides a fused heterocyclic polymer having any one of the following structural formulas:

[0008] Wherein, n is 10 to 500; R 1 R 1’ R 1” R 2 Each is independently selected from either aromatic or aliphatic groups. In this application, n is an integer, and by way of example, n is 10, 20, 30, 40, 60, 100, 150, 200, 300, 400, 500, or within any two of the above values.

[0009] The fused heterocyclic polymer satisfies at least one of (1) to (5):

[0010] (1) The R1 Choose one of the following structural formulas:

[0011] The values ​​of m, h, j, k, and l are 1–20, h, j, k, and l, respectively; Y is selected from at least one of NH, O, or S; * indicates the substitution position; m, h, j, k, and l are integers; it should be noted that the substitution positions in structural formulas 1, 2, and 3 include ortho substitution, meta substitution, or para substitution.

[0012] (2) The R 1’ Choose one of the following structural formulas:

[0013] * indicates a replacement position;

[0014] (3) The R 1” Choose one of the following structural formulas:

[0015] * indicates a replacement position;

[0016] (4) The R 2 Choose one of the following structural formulas:

[0017] The value of o is 1 to 20, and the value of p is 1 to 20; * indicates the substitution position;

[0018] (5) The R 3 It is selected from at least one of H, CH3, Br or OCH3.

[0019] The fused heterocyclic polymer has any one of the following structural formulas:

[0020] This application provides a method for preparing a fused heterocyclic polymer, comprising:

[0021] (1) Under normal pressure and CO2 atmosphere, terminal alkyne compounds and dihalides undergo polymerization to obtain intermediate products;

[0022] (2) N-hydroxyphthalimide and its derivatives are added to the intermediate product to carry out a polymerization reaction.

[0023] It should be noted that a CO2-containing atmosphere includes a pure CO2 atmosphere; a CO2-containing atmosphere can also include other atmospheres. The volume percentage of CO2 in a CO2-containing atmosphere is not less than 90%.

[0024] Furthermore, the terminal alkyne compound has any one of the following structural formulas:

[0025] The R 1 Choose one of the following structural formulas:

[0026] The R 1’ Choose one of the following structural formulas:

[0027] The R 1” Choose one of the following structural formulas:

[0028] The values ​​of m, h, j, k, and l are 1–20; the value of Y is selected from at least one of NH, O, or S; * indicates a substitution position; and / or,

[0029] The N-hydroxyphthalimide and its derivatives have the following structural formula:

[0030] Among them, R 3 At least one selected from H, CH3, Br, or OCH3; and / or,

[0031] The dihalide has the following structural formula:

[0032] Wherein, X is a halogen element;

[0033] Optionally, X includes bromine, chlorine, or iodine;

[0034] Optionally, the R 2 Choose one of the following structural formulas:

[0035] The value of o is 1 to 20, and the value of p is 1 to 20; * indicates the substitution position.

[0036] Furthermore, the terminal alkyne compound has any one of the following structural formulas:

[0037] And / or,

[0038] The N-hydroxyphthalimide and its derivatives have any one of the following structural formulas:

[0039] Further, in step (1), the molar ratio of the alkynyl group in the terminal alkyne compound to the halogen element in the dihalogen compound is (0.8–1.2):(0.8–1.2); and / or,

[0040] The molar ratio of the N-hydroxyphthalimide and its derivatives to the terminal alkyne compound is (1–10):1; and / or,

[0041] In step (1), the polymerization reaction is carried out at a temperature of room temperature to 100°C for a time of 6 to 24 hours; and / or,

[0042] In step (2), the polymerization reaction is carried out at a temperature of room temperature to 80°C for a time of 1 to 10 hours; and / or,

[0043] In step (1), the polymerization reaction is carried out at a temperature of room temperature to 60°C for 22 to 24 hours; and / or,

[0044] In step (2), the polymerization reaction is carried out at a temperature of room temperature to 60°C for 2 to 4 hours.

[0045] Furthermore, step (1) further includes adding at least one of a solvent and a catalyst before carrying out the polymerization reaction;

[0046] Optionally, the solvent includes at least one selected from dichloromethane, chloroform, toluene, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide;

[0047] Optionally, the catalyst includes at least one of triphenylphosphine, a copper catalyst, and an alkaline catalyst;

[0048] Optionally, the copper catalyst includes at least one of cuprous iodide, cuprous bromide, cuprous chloride, cuprous acetate, and cuprous sulfate;

[0049] Optionally, the alkaline catalyst comprises at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, triethylenediamine, 1,8-diazabicycloundec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 4-dimethylaminopyridine, tetramethylethylenediamine, N-methylmorpholine, potassium tert-butoxide, sodium tert-butoxide, and n-butyllithium.

[0050] Furthermore, the catalyst comprises triphenylphosphine, a copper catalyst, and a base catalyst; and / or,

[0051] The molar ratio of triphenylphosphine to copper catalyst is (0.8–1.1):1; and / or,

[0052] The molar ratio of the copper catalyst to the terminal alkyne compound is (1-10):10; and / or,

[0053] The molar ratio of the alkaline catalyst to the terminal alkyne compound is (4–8):1; and / or,

[0054] The concentration of the terminal alkyne compound in the solvent is 0.1–0.5 mol / L.

[0055] Step (2) is followed by a precipitation and drying step of the crude product; specifically, the crude product is mixed with an organic solvent, a precipitant is added for precipitation, the precipitate is collected, and dried to constant weight. The organic solvent includes, but is not limited to, at least one of dichloromethane, chloroform, and tetrahydrofuran. The precipitant includes, but is not limited to, at least one of water, methanol, ethanol, n-hexane, petroleum ether, diethyl ether, and acetone. Drying is performed under vacuum at a temperature of 25–80°C.

[0056] This application also provides an application of the above-mentioned fused heterocyclic polymer or the fused heterocyclic polymer prepared by the above-mentioned preparation method in optical materials or metal ion detection;

[0057] Optionally, the fused heterocyclic polymer is used to detect Ag. + ;

[0058] Optionally, the fused heterocyclic polymer can be used as a fluorescent material.

[0059] The technical solution of this application has the following advantages:

[0060] 1. The fused heterocyclic polymer provided in this application is prepared directly using carbon dioxide under normal pressure, realizing the resource utilization of CO2. This fused heterocyclic polymer exhibits high thermal stability and excellent processability, showing promising application prospects. The polymer displays bright fluorescence in both solution and aggregated states, making it suitable for optical materials. The fused heterocyclic polymer of this application is compatible with Ag... + Fluorescence quenching after action enables qualitative detection of metallic Ag. + Specifically, this fused heterocyclic polymer incorporates aggregation-induced emission (AIE) groups, endowing it with AIE properties and unique post-aggregation luminescence enhancement characteristics. It shows great potential in organic light-emitting diodes (OLEDs) and is an ideal light-emitting material for undoped OLED devices. Fused heterocyclic polymers with AIE properties also have applications in fluorescence sensors. Their luminescence properties can be precisely controlled by light stimulation, showing great promise in fields such as bioimaging, anti-counterfeiting, optical patterning, and optical sensors. For example, they can be used as fluorescent probes, exhibiting high photostability and biocompatibility.

[0061] 2. The method for preparing fused heterocyclic polymers provided in this application yields polyoxazolidinones with a clear structure and 100% grafting rate. The polymerization reaction is carried out directly under ambient pressure using carbon dioxide, terminal alkynes, dihalides, and N-hydroxyphthalimide and its derivatives, especially NHPI. The reaction conditions are mild, the process is simple, and the polymerization efficiency is high. High-yield and high-molecular-weight polymers can be obtained at relatively low temperatures, and the polymers exhibit high thermal stability and excellent processability. The dihalides can be chlorides, bromides, or iodides, demonstrating broad applicability to different raw materials. This application achieves CO2 fixation and simultaneously prepares fused-ring polymers through multi-component tandem polymerization, and these fused-ring polymers can be applied in the field of fluorescent probes.

[0062] This application uses dihalides with a specific structure, which have better stability and are not easily decomposed or deteriorated under normal conditions. They are also less sensitive to water and alcohols, and do not require overly strict anhydrous and oxygen-free environments for storage and use. Dihalides also have high reactivity. Compared with ordinary diacyl chlorides, which have many side reactions and low product selectivity, dihalides have moderate reactivity, achieving higher reaction selectivity and higher yield of the target product. Attached Figure Description

[0063] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0064] Figure 1 is a thermogravimetric diagram of the fused heterocyclic polymer P1 in Example 1 of this application;

[0065] Figure 2 is a differential scanning spectroscopy (DSS) spectrum of the fused heterocyclic polymer P1 in Example 1 of this application;

[0066] Figure 3 is the spectrum of the fused heterocyclic polymer P1 in the mixed solvent of Example 1 of this application;

[0067] Figure 4 is a schematic diagram showing the interaction between polymer P1 in Example 1 of this application and metal ions in a mixed solvent;

[0068] Figure 5 shows the effect of the polymer of Example 1 of this application on different concentrations of Ag. + The test results of the ion quenching reaction are shown in the figure; the left figure shows the effect of polymer P1 on different concentrations of Ag. + The fluorescence intensity response diagram, the right figure shows the relative PL intensity (I0 / I) at 512 nm and Ag. + Linear relationship graph of concentration;

[0069] Figure 6 is the proton spectrum of fused heterocyclic polymer P3, monomer 1b, and monomer 2a in Example 3 of this application;

[0070] Figure 7 is the carbon spectrum of fused heterocyclic polymer P3, monomer 1b, and monomer 2a in Example 3 of this application. Detailed Implementation

[0071] The following embodiments are provided to better understand this application and are not limited to the preferred embodiments described herein. They do not constitute a limitation on the content and scope of protection of this application. Any product that is the same as or similar to this application, derived by anyone under the guidance of this application or by combining features of this application with other prior art, falls within the scope of protection of this application.

[0072] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0073] Example 1

[0074] This embodiment provides a method for preparing polyoxazolidinone, including the following steps:

[0075] (1) The terminal alkyne compound 1a has the following structural formula, and its preparation method is described in the literature Polym. Chem., 2017, 8, 2713-2722. The dihalide 2a is 1,6-dibromohexane (commercially available, purchased from Anage Chemicals).

[0076] In a 25 mL dry Schlenk reaction tube, a magnetic ion, monomer 1a (76 mg, 0.2 mmol), and Ph3P (10.48 mg, 0.04 mmol) were added. Then, in an argon-protected glove box, CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) were added. The polymerization tube, sealed with a rubber stopper, was removed from the glove box, and a vacuum was applied (30 min). Nitrogen was replaced once (1 min), and a vacuum was applied again. Dry DMF (1 mL) was injected into the tube using a syringe, and a vacuum was applied again. A CO2 balloon was inserted through a needle, and 2a (30.77 μl, 0.2 mmol) was injected into the tube using a microsyringe. The polymerization tube was placed in a 60 °C heated metal block and stirred for 24 h (400 r / min). After the reaction was completed and cooled to room temperature, the intermediate product was obtained.

[0077] (2) Dissolve NHPI (NHPI to monomer 1a molar ratio of 6:1) in ultra-dry DMF (1 mL), inject into the system using a syringe, and react at room temperature for 3 h. After the reaction is complete, a crude product reaction solution is obtained. Dilute the reaction solution with dichloromethane to 5 mL to obtain a polymer solution; under stirring at 600 r / min, add the polymer solution dropwise to methanol, let stand for 4 h, filter, and vacuum dry at 50 °C to constant weight to obtain the fused heterocyclic polymer P1, whose structural formula is as follows.

[0078] The yield of fused heterocyclic polymer P1 was determined to be 65%, with a weight-average molecular weight of 20,500 and a molecular weight distribution of 1.55. Fused heterocyclic polymer P1 was dispersed in DMF solvent and aggregated in DMF aqueous solution (water to DMF volume ratio 1:1). The concentration of P1 in the DMF aqueous solution was 10... -5 M, and exhibiting good fluorescence emission, suggests that this fused heterocyclic polymer (FRP) can be applied in the field of luminescence. Furthermore, the FRP P1 is readily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, and DMSO at room temperature, indicating excellent solubility and processability. Figure 1 shows the thermogravimetric analysis (TGA) of P1, with a thermal decomposition temperature (the temperature at which 5% weight loss occurs) of 226℃. Figure 2 shows the differential scanning spectroscopy (DSS) of P1, with a glass transition temperature of 148℃, demonstrating that the prepared FRP P1 has good thermal stability.

[0079] Figure 3 (left) shows the spectrum of polymer P1 in a mixed solvent (the mixed solvent includes water and DMF in different volume ratios). w The volume percentage of water in the mixed solvent is represented. Figure 3 (right) shows the relationship between the relative intensity (I / I0) of polymer P1 in the mixed solvent (which includes water and DMF in different volume ratios) and the volume percentage of water in the mixed solvent, where I is the peak intensity of the mixed solvent and I0 is the peak intensity of pure DMF. The fluorescence spectrum of polymer P1 in pure DMF is almost parallel to the horizontal axis, indicating that polymer P1 emits almost no light in pure DMF solution. As the water content in the system gradually increases, the polymer chains begin to aggregate, and the fluorescence gradually increases. The maximum fluorescence intensity of polymer P1 appears at f w In a 50% mixed solvent, the maximum fluorescence intensity of polymer P1 was 35.1 times that in pure DMF solution. This demonstrates that polymer P1, containing tetraphenylethylene (TPE) groups, exhibits typical aggregation-induced emission (AIE) characteristics.

[0080] Figure 4 is a schematic diagram of the interaction between polymer P1 and metal ions in a mixed solvent. Figure 4a shows the relative PL intensity (I0 / I) of polymer P1 after interacting with different metal ions in a mixed solvent (DMF to water volume ratio of 1:1) for 120 min. Under the same conditions, Fe... 3+ Ag + Ca 2+ Cd 2+ Ce 3+ Co 2+ Cr 3+ Cu 2+ Dy 3+ Fe 2+ K + Lu 2+ Mg 2+ Na + NH4 + Ni 2+ ,Sc 3+ 、Sm 3+ 、Sr 2+ Y 3+ Yb 6+ Zn 2+ We mixed 22 kinds of metal cations with polymer P1 nanoclusters. Surprisingly, we found that, including Fe... 3+ The fluorescence of 22 ions, including Ag, did not show significant changes, but after 2 hours of observation, Ag... + Ions gradually darken the color of the probe solution under sunlight (see Figure 4b), and the fluorescence of the probe weakens under ultraviolet light (Figure 4c).

[0081] In addition, in order to study the effect of this polymer on Ag + The sensitivity of the polymer to ion quenching reactions was investigated by titration experiments with silver ions on the fused heterocyclic polymer P1. The polymer responded to different concentrations of Ag. + The test results for the ion quenching reaction are shown in Figure 5. The left side of Figure 5 shows the effect of polymer P1 on different concentrations of Ag. + The fluorescence intensity response diagram, the right figure shows the relative PL intensity (I0 / I) at 512 nm and Ag. + Linear relationship graph of concentration. Records different concentrations of Ag. + The relative PL intensity (I0 / I) after 120 minutes of interaction between the ions and the polymer probe, with Ag + The curve formed by plotting ion concentration on the x-axis and relative PL intensity (I0 / I) on the y-axis is shown in the right part of Figure 5. The relative PL intensity (I0 / I) and [Ag]... + The Stern-Volmer curves of the sample showed a good linear relationship, and the quenching constant was calculated to be 2980 M using the formula. -1The LOD is 4.90×10 -6 M indicates that the fused heterocyclic polymer can perform trace qualitative detection of silver ions.

[0082] Example 2

[0083] This embodiment provides a method for preparing a fused heterocyclic polymer, including the following steps:

[0084] (1) Terminal alkyne compound 1a is the same as in Example 1. Dihalide 2b is 1,4-dichlorobenzyl (commercially available, purchased from Anage Chemicals).

[0085] In a 25 mL dry Schlenk reaction tube, a magnetic ion, monomer 1a (76 mg, 0.2 mmol), Ph3P (10.48 mg, 0.04 mmol), and 2b (35.01 mg, 0.2 mmol) were added. Then, in an argon-protected glove box, CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) were added. The polymerization tube, sealed with a rubber stopper, was removed from the glove box, and a vacuum was applied (30 min). Nitrogen was replaced once (1 min), and a vacuum was applied again. Dry DMF (1 mL) was injected into the tube using a syringe, and a vacuum was applied again. A CO2 balloon was inserted using a needle. The polymerization tube was placed in a 60 °C heated metal block and stirred for 24 h (400 r / min). After the reaction cooled to room temperature, the intermediate product was obtained.

[0086] (2) Dissolve NHPI (molar ratio of NHPI to monomer 1a is 6:1) in ultra-dry DMF (1 mL), inject it into the system with a syringe, and react at room temperature for 3 h. After the reaction is completed, crude product reaction solution is obtained. Dilute the reaction solution with dichloromethane to 5 mL to obtain polymer solution. Under stirring at 600 r / min, polymer solution is added dropwise to methanol, then allowed to stand for 4 h, filtered, and vacuum dried at 50 °C to constant weight to obtain fused heterocyclic polymer P2, with the following structural formula.

[0087] The yield of the fused heterocyclic polymer P2 was determined to be 82%, with a weight-average molecular weight of 39,800 and a molecular weight distribution of 2.30. P2 exhibited good fluorescence emission in both DMF solvent and aqueous DMF solution (water to DMF volume ratio 7:3) at a concentration of 10... -5 Furthermore, this fused heterocyclic polymer is readily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0088] Example 3

[0089] This embodiment provides a method for preparing a fused heterocyclic polymer, including the following steps:

[0090] (1) Terminal alkyne compound 1b has the following structural formula, and the synthesis method is the same as in Example 1. The dihalide is the same as in Example 1.

[0091] In a 25 mL dry Schlenk reaction tube, a magnetic ion, monomer 1b (58.66 mg, 0.2 mmol), and Ph3P (10.48 mg, 0.04 mmol) were added. Then, in an argon-protected glove box, CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) were added. The polymerization tube, sealed with a rubber stopper, was removed from the glove box, and a vacuum was applied (30 min). Nitrogen was replaced once (1 min), and a vacuum was applied again. Dry DMF (1 mL) was injected into the tube using a syringe, and a vacuum was applied again. A CO2 balloon was inserted through a needle, and 2a (30.77 μl, 0.2 mmol) was injected into the tube using a microsyringe. The polymerization tube was placed in a 60 °C heated metal block and stirred for 24 h (400 r / min). After the reaction cooled to room temperature, the intermediate product was obtained.

[0092] (2) Dissolve NHPI (NHPI to monomer 1b molar ratio of 6:1) in ultra-dry DMF (1 mL), inject it into the system with a syringe, and react at room temperature for 3 h. After the reaction is completed, crude product reaction solution is obtained. Dilute the reaction solution with dichloromethane to 5 mL to obtain polymer solution. Under stirring at 600 r / min, polymer solution is added dropwise to methanol, then allowed to stand for 4 h, filtered, and vacuum dried at 50 °C to constant weight to obtain fused heterocyclic polymer P3, with the following structural formula.

[0093] The yield of fused heterocyclic polymer P3 was determined to be 76%, with a weight-average molecular weight of 23,500 and a molecular weight distribution of 1.71. Figure 6 shows the proton NMR spectra of fused heterocyclic polymer P3, monomer 1b, and monomer 2a; where A is the proton NMR spectrum of monomer 1b, B is the proton NMR spectrum of monomer 2a, C is the NHPI proton NMR spectrum, D is the proton NMR spectrum of the model compound (the structural formula of the model compound is shown below, and the preparation method is based on the literature Green Chem., 2015, 17, 4061-4067), and E is the proton NMR spectrum of fused heterocyclic polymer P3. Figure 7 shows the carbon NMR spectra of fused heterocyclic polymer P3, monomer 1b, and monomer 2a; where A is the carbon NMR spectrum of monomer 1b, B is the carbon NMR spectrum of monomer 2a, C is the NHPI carbon NMR spectrum, D is the carbon NMR spectrum of the model compound, and E is the carbon NMR spectrum of fused heterocyclic polymer P3.

[0094] Figure 6 shows the structure of the fused heterocyclic polymer P3 and the monomer 1b. 1The NMR peak of alkyne hydrogen in ¹H NMR is at δ 4.02. In the spectra of the model compound (Figure 6, C) and polymer P3 (Figure 6, E), the NMR peak of alkyne hydrogen disappears, while a characteristic NMR peak of methylene hydrogen near the ester group appears at δ 4.09. As shown in Figure 7, the NMR peak representing the triple-bonded carbon in monomer 1b (Figure 7, A) is retained in polymer P3, but disappears in the model compound (Figure 7, C) and polymer P3 (Figure 7, E). This is because the introduced NHPI (Figure 7, D) reacts with the carbon-carbon triple bond, undergoing cyclization to form an isoxazole isoindole structure. In polymer P3… 13 In the C10 NMR spectrum, not only were the carbonyl carbons that did not react with NHPI and the methylene carbons near the ester groups retained, with corresponding NMR peaks appearing at δ161.33 and δ64.40, respectively, but the NMR peak of the carbonyl carbon in the newly formed isoindole ring also appeared at δ167.70. This indicates that the polymerization reaction proceeded successfully and exhibited excellent post-modification grafting efficiency.

[0095] Example 4

[0096] This embodiment provides a method for preparing a fused heterocyclic polymer, including the following steps:

[0097] (1) Terminal alkyne compound 1b is the same as in Example 3. Dihalide 2b is 1,4-p-dichlorobenzene (commercially available, purchased from Anage Chemicals).

[0098] In a 25 mL dry Schlenk reaction tube, a magnetic ion, monomer 1b (58.66 mg, 0.2 mmol), Ph3P (10.48 mg, 0.04 mmol), and 2b (35.01 mg, 0.2 mmol) were added. Then, in an argon-protected glove box, CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) were added. The polymerization tube, sealed with a rubber stopper, was removed from the glove box, and a vacuum was applied (30 min). Nitrogen was replaced once (1 min), and a vacuum was applied again. Dry DMF (1 mL) was injected into the tube using a syringe, and a vacuum was applied again. A CO2 balloon was inserted using a needle. The polymerization tube was placed in a 60 °C heated metal block and stirred for 24 h (400 r / min). After the reaction cooled to room temperature, the intermediate product was obtained.

[0099] (2) Dissolve NHPI (NHPI to monomer 1b molar ratio of 6:1) in ultra-dry DMF (1 mL), inject into the system using a syringe, and react at room temperature for 3 h. After the reaction is complete, a crude product reaction solution is obtained. Dilute the reaction solution with dichloromethane to 5 mL to obtain a polymer solution; under stirring at 600 r / min, add the polymer solution dropwise to methanol, let stand for 4 h, filter, and vacuum dry at 50 °C to constant weight to obtain the fused heterocyclic polymer P4, with the following structural formula.

[0100] The yield of fused heterocyclic polymer P4 was determined to be 80%, with a weight-average molecular weight of 33,200 and a molecular weight distribution of 2.21. This fused heterocyclic polymer P4 is readily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0101] Example 5

[0102] This embodiment provides a method for preparing a fused heterocyclic polymer, including the following steps:

[0103] (1) Terminal alkyne compound 1c, which was synthesized in the same way as in Example 1, and has the following structural formula. The terminal alkyne compound is a white solid with a yield of 82%. Dihalide 2a is 1,6-dibromohexane (commercially available, purchased from Anage Chemicals).

[0104] In a 25 mL dry Schlenk reaction tube, a magnetic ion, monomer 1c (90.4 mg, 0.2 mmol), and Ph3P (10.48 mg, 0.04 mmol) were added. Then, in an argon-protected glove box, CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) were added. The polymerization tube, sealed with a rubber stopper, was removed from the glove box, and a vacuum was applied (30 min). Nitrogen was replaced once (1 min), and a vacuum was applied again. Dry DMF (1 mL) was injected into the tube using a syringe, and a vacuum was applied again. A CO2 balloon was inserted through a needle, and 2a (30.77 μl, 0.2 mmol) was injected into the tube using a microsyringe. The polymerization tube was placed in a 60 °C heated metal block and stirred for 24 h (400 r / min). After the reaction cooled to room temperature, the intermediate product was obtained.

[0105] (2) NHPI (NHPI to monomer 1c molar ratio of 6:1) was dissolved in ultra-dry DMF (1 mL). The solution was injected into the system using a syringe and reacted at room temperature for 3 h. After the reaction, a crude product reaction solution was obtained. The reaction solution was diluted to 5 mL with dichloromethane to obtain a polymer solution. Under stirring at 600 r / min, the polymer solution was added dropwise to methanol, then allowed to stand for 4 h, filtered, and dried under vacuum at 50 °C to constant weight to obtain the fused heterocyclic polymer P5, with the following structural formula.

[0106] The yield of the fused heterocyclic polymer P5 was determined to be 75%, with a weight-average molecular weight of 28,000 and a molecular weight distribution of 1.93. P5 is readily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0107] Example 6

[0108] This embodiment provides a method for preparing a fused heterocyclic polymer, including the following steps:

[0109] (1) Terminal alkyne compound 1c is the same as in Example 5. Dihalide 2b is 1,4-dichlorobenzyl (commercially available, purchased from Anage Chemicals).

[0110] In a 25 mL dry Schlenk reaction tube, a magnetic ion, monomer 1c (90.4 mg, 0.2 mmol), Ph3P (10.48 mg, 0.04 mmol), and 2b (35.01 mg, 0.2 mmol) were added. Then, in an argon-protected glove box, CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) were added. The polymerization tube, sealed with a rubber stopper, was removed from the glove box, and a vacuum was applied (30 min). Nitrogen was replaced once (1 min), and a vacuum was applied again. Dry DMF (1 mL) was injected into the tube using a syringe, and a vacuum was applied again. A CO2 balloon was inserted using a needle. The polymerization tube was placed in a 60 °C heated metal block and stirred for 24 h (400 r / min). After the reaction cooled to room temperature, the intermediate product was obtained.

[0111] (2) NHPI (NHPI to monomer 1c molar ratio of 6:1) was dissolved in ultra-dry DMF (1 mL). The solution was injected into the system using a syringe and reacted at room temperature for 3 h. After the reaction was completed, a crude product reaction solution was obtained. The reaction solution was diluted to 5 mL with dichloromethane to obtain a polymer solution. The polymer solution was added dropwise to methanol under stirring at 600 r / min, then allowed to stand for 4 h, filtered, and dried under vacuum at 50 °C to constant weight to obtain the fused heterocyclic polymer P6, with the following structural formula.

[0112] The yield of the fused heterocyclic polymer P6 was determined to be 85.5%, with a weight-average molecular weight of 42,700 and a molecular weight distribution of 2.68. P6 is readily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0113] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A fused heterocyclic polymer, characterized in that, It has any of the following structures: Wherein, n is 10 to 500; R 1 R 1’ R 1” R 2 Each group is independently selected from either aromatic or aliphatic groups.

2. The fused heterocyclic polymer according to claim 1, characterized in that, Satisfy at least one of (1) to (5): (1) The R 1 Choose one of the following structural formulas: The values ​​of m, h, j, k, and l are 1–20; the value of Y is selected from at least one of NH, O, or S; * indicates a substitution position; (2) The R 1’ Choose one of the following structural formulas: * indicates a replacement position; (3) The R 1” Choose one of the following structural formulas: * indicates a replacement position; (4) The R 2 Choose one of the following structural formulas: The value of o is 1 to 20, and the value of p is 1 to 20; * indicates the substitution position; (5) The R 3 It is selected from at least one of H, CH3, Br or OCH3.

3. The fused heterocyclic polymer according to claim 1 or 2, characterized in that, The fused heterocyclic polymer has any one of the following structural formulas:

4. A method for preparing a fused heterocyclic polymer, characterized in that, include: (1) Under normal pressure and CO2 atmosphere, terminal alkyne compounds and dihalides undergo polymerization to obtain intermediate products; (2) N-hydroxyphthalimide and its derivatives are added to the intermediate product to carry out a polymerization reaction.

5. The preparation method according to claim 4, characterized in that, The terminal alkyne compound has any one of the following structural formulas: Preferably, the R 1 Choose one of the following structural formulas: Preferably, the R 1’ Choose one of the following structural formulas: Preferably, the R 1” Choose one of the following structural formulas: The values ​​of m, h, j, k, and l are 1–20; the value of Y is selected from at least one of NH, O, or S; * indicates a substitution position; and / or, The N-hydroxyphthalimide and its derivatives have the following structural formula: Among them, R 3 At least one selected from H, CH3, Br, or OCH3; and / or, The dihalide has the following structural formula: X-R 2 -X Wherein, X is a halogen element; Preferably, X comprises bromine, chlorine, or iodine; Preferably, the R 2 Choose one of the following structural formulas: The value of o is 1 to 20, and the value of p is 1 to 20; * indicates the substitution position.

6. The preparation method according to claim 4 or 5, characterized in that, The terminal alkyne compound has any one of the following structural formulas: And / or, The N-hydroxyphthalimide and its derivatives have any one of the following structural formulas:

7. The preparation method according to any one of claims 4 to 6, characterized in that, In step (1), the molar ratio of the alkynyl group in the terminal alkyne compound to the halogen element in the dihalogen compound is (0.8–1.2):(0.8–1.2); and / or, The molar ratio of the N-hydroxyphthalimide and its derivatives to the terminal alkyne compound is (1–10):1; and / or, In step (1), the polymerization reaction is carried out at a temperature of room temperature to 100°C for a time of 6 to 24 hours; and / or, In step (2), the polymerization reaction is carried out at a temperature of room temperature to 80°C for a time of 1 to 10 hours; and / or, In step (1), the polymerization reaction is carried out at a temperature of room temperature to 60°C for 22 to 24 hours; and / or, In step (2), the polymerization reaction is carried out at a temperature of room temperature to 60°C for 2 to 4 hours.

8. The preparation method according to claim 4, characterized in that, Step (1) further includes adding at least one of a solvent and a catalyst before carrying out the polymerization reaction; Preferably, the solvent includes at least one selected from dichloromethane, chloroform, toluene, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide; Preferably, the catalyst comprises at least one of triphenylphosphine, a copper catalyst, and an alkaline catalyst; Preferably, the copper catalyst includes at least one of cuprous iodide, cuprous bromide, cuprous chloride, cuprous acetate, and cuprous sulfate; Preferably, the alkaline catalyst comprises at least one selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, triethylenediamine, 1,8-diazabicycloundec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 4-dimethylaminopyridine, tetramethylethylenediamine, N-methylmorpholine, potassium tert-butoxide, sodium tert-butoxide, and n-butyllithium.

9. The preparation method according to claim 8, characterized in that, The catalyst includes triphenylphosphine, a copper catalyst, and a base catalyst; and / or, The molar ratio of triphenylphosphine to copper catalyst is (0.8–1.1):1; and / or, The molar ratio of the copper catalyst to the terminal alkyne compound is (1-10):10; and / or, The molar ratio of the alkaline catalyst to the terminal alkyne compound is (4–8):1; and / or, The concentration of the terminal alkyne compound in the solvent is 0.1–0.5 mol / L.

10. The application of the fused heterocyclic polymer according to any one of claims 1 to 3 or the fused heterocyclic polymer prepared by the preparation method according to any one of claims 4 to 9 in optical materials or metal ion detection; Preferably, the fused heterocyclic polymer is used for the detection of Ag. + ; Preferably, the fused heterocyclic polymer is used as a fluorescent material.

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