Fused heterocyclic polymer and preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer material preparation, and particularly relates to a fused heterocyclic polymer as well as a preparation method and application thereof. The fused heterocyclic polymer has a special structure, high thermal stability and excellent processability, and has a good application prospect. The polymer shows bright fluorescence in a solution state or an aggregation state, and can be used for optical materials. After the fused heterocyclic polymer reacts with Ag < + >, fluorescence is quenched, and metal Ag < + > ions can be qualitatively detected.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material preparation, and in particular relates to a condensed heterocyclic polymer and a preparation method and application thereof. Background Art

[0002] Carbon dioxide is a major greenhouse gas, and its excessive emission will lead to global warming. Converting CO2 into useful chemicals, such as polycarbonate, polyurethane and condensed heterocyclic polymers, can not only reduce the concentration of CO2 in the atmosphere and alleviate the greenhouse effect, but also achieve the recycling of resources. This conversion process embodies the concept of "carbon capture and utilization" (CCU). As an abundant, non-toxic, low-cost and sustainable C1 raw material, CO2 can be converted into high-value-added chemicals through multi-component polymerization (MCP), which not only helps to reduce environmental pollution, but also promotes sustainable economic development. How to make better use of CO2 is of great significance. Summary of the invention

[0003] Therefore, the technical problem to be solved by the present invention is to overcome the above technical problems, thereby providing a fused heterocyclic polymer and a preparation method and application thereof.

[0004] To this end, the present invention provides the following technical solutions.

[0005] The present invention provides a fused heterocyclic polymer having any one of the following structural formulas:

[0006]

[0007] Wherein, n is 10 to 500; R 1 , R 1’ , R 1” , R 2 The value of n in the present invention is an integer, and for example, n is 10, 20, 30, 40, 60, 100, 150, 200, 300, 400, 500 or a range formed by any two of the above values.

[0008] The fused heterocyclic polymer satisfies at least one of (1) to (5):

[0009] (1) R 1 Select one of the following structural formulas:

[0010]

[0011] The m is 1 to 20, h is 1 to 20, j is 1 to 20, k is 1 to 20, and l is 1 to 20; the Y is selected from at least one of NH, O, or S; * represents the substitution position; m, h, j, k, and l are integers; it should be explained that the substitution position in Structural Formula 1, Structural Formula 2, and Structural Formula 3 includes ortho-substitution, meta-substitution, or para-substitution;

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

[0013]

[0014] * indicates a replacement position;

[0015] (3) R 1” Select one of the following structural formulas:

[0016]

[0017] * indicates a replacement position;

[0018] (4) R 2 Select one of the following structural formulas:

[0019]

[0020] The oo is 1 to 20, the p is 1 to 20; * indicates the substitution position;

[0021] (5) R 3 At least one selected from H, CH3, Br or OCH3. The fused heterocyclic polymer has any one of the following structural formulas:

[0022]

[0023] The present invention provides a method for preparing a condensed heterocyclic polymer, comprising:

[0024] (1) Under normal pressure and a CO2-containing atmosphere, a terminal alkyne compound and a dihalide undergo a polymerization reaction to obtain an intermediate product;

[0025] (2) Adding N-hydroxyphthalimide and its derivatives to the intermediate product to carry out a polymerization reaction.

[0026] It should be noted that the CO2-containing atmosphere includes a pure CO2 atmosphere; the CO2-containing atmosphere may also include other atmospheres. The volume proportion of CO2 in the CO2-containing atmosphere is not less than 90%.

[0027] Furthermore, the terminal alkyne compound has any one of the following structural formulas:

[0028]

[0029] The R 1 Select one of the following structural formulas:

[0030]

[0031] The R 1’ Select one of the following structural formulas:

[0032]

[0033] The R 1” Select one of the following structural formulas:

[0034]

[0035] The m is 1 to 20, h is 1 to 20, j is 1 to 20, k is 1 to 20, and l is 1 to 20; the Y is selected from at least one of NH, O or S; * indicates a substitution position; and / or,

[0036] The N-hydroxyphthalimide and its derivatives have the following structural formula:

[0037]

[0038] Among them, R 3 At least one selected from H, CH3, Br or OCH3; and / or,

[0039] The dihalide has the following structural formula:

[0040] XR 2 -X

[0041] Wherein, X is a halogen element;

[0042] Preferably, said X comprises bromine, chlorine or iodine;

[0043] Preferably, the R 2 Select one of the following structural formulas:

[0044]

[0045] The o is 1 to 20, the p is 1 to 20, and * indicates a substitution position.

[0046] Furthermore, the terminal alkyne compound has any one of the following structural formulas:

[0047]

[0048] and / or,

[0049] The N-hydroxyphthalimide and its derivatives have any one of the following structural formulas:

[0050]

[0051] Further, in the 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 to 1.2):(0.8 to 1.2); and / or,

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

[0053] In the step (1), the polymerization reaction temperature is from room temperature to 100° C. and the reaction time is from 6 to 24 hours; and / or,

[0054] In step (2), the polymerization reaction temperature is room temperature to 80° C., and the reaction time is 1 to 10 hours; and / or,

[0055] In the step (1), the polymerization reaction temperature is room temperature to 60° C. and the reaction time is 22 to 24 hours; and / or,

[0056] In the step (2), the polymerization reaction temperature is room temperature to 60° C., and the reaction time is 2 to 4 hours.

[0057] Furthermore, the step (1) further comprises adding at least one of a solvent and a catalyst before carrying out the polymerization reaction;

[0058] Preferably, the solvent comprises at least one of dichloromethane, chloroform, toluene, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide and N,N-dimethylformamide;

[0059] Preferably, the catalyst comprises at least one of triphenylphosphine, a copper catalyst and a base catalyst;

[0060] Preferably, the copper catalyst comprises at least one of cuprous iodide, cuprous bromide, cuprous chloride, cuprous acetate and cuprous sulfate;

[0061] Preferably, the base catalyst includes 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.

[0062] Further, the catalyst comprises triphenylphosphine, a copper catalyst and a base catalyst; and / or,

[0063] The molar ratio of triphenylphosphine to copper catalyst is (0.8-1.1):1; and / or,

[0064] The molar ratio of the copper catalyst to the terminal alkyne compound is (1-10):10; and / or,

[0065] The molar ratio of the base catalyst to the terminal alkyne compound is (4-8):1; and / or,

[0066] The concentration of the terminal alkyne compound in the solvent is 0.1 to 0.5 mol / L.

[0067] After step (2), the step of precipitating and drying the crude product is also included; specifically, the crude product is mixed with an organic solvent, a precipitant is added for precipitation, the precipitate is collected, and the precipitate is dried to a 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, ether and acetone. The drying is vacuum drying at a temperature of 25 to 80°C.

[0068] The present invention also provides an application of the above fused heterocyclic polymer or the fused heterocyclic polymer prepared by the above preparation method in optical material or metal ion detection;

[0069] Preferably, the fused heterocyclic polymer is used to detect Ag + ;

[0070] Preferably, the fused heterocyclic polymer is used as a fluorescent material.

[0071] The technical solution of the present invention has the following advantages:

[0072] 1. The condensed heterocyclic polymer provided by the present invention is directly prepared by using carbon dioxide under normal pressure conditions, realizing the resource utilization of CO2. The condensed heterocyclic polymer has high thermal stability and excellent processability, and has good application prospects. The polymer shows bright fluorescence in solution or aggregate state, and can be used in optical materials. + After the reaction, the fluorescence is quenched, and metal Ag can be qualitatively detected +ions. Specifically, the condensed heterocyclic polymer introduces aggregation-induced emission (AIE characteristic) groups, giving the polymer AIE characteristics, and has unique luminescence enhancement characteristics after aggregation, showing great potential in organic light-emitting diodes, and is an ideal luminescent material for non-doped OLED devices. Condensed heterocyclic polymers with AIE characteristics are also used in the field of fluorescent sensors, and their luminescence properties can be precisely controlled by light stimulation, showing great application prospects in the fields of bioimaging, anti-counterfeiting, light patterning and optical sensors. For example, they can be used as fluorescent probes, etc., with high photostability and biocompatibility.

[0073] 2. The preparation method of the fused heterocyclic polymer provided by the present invention, the obtained polyoxazolidinone has a clear structure and a 100% grafting rate, and directly uses carbon dioxide, terminal alkyne compounds, dihalides and N-hydroxyphthalimide and its derivatives, especially NHPI, to carry out polymerization reaction at normal pressure, and the reaction conditions are mild, the process is simple, and the polymerization efficiency is high. A polymer with high yield and high molecular weight can be obtained at a relatively low temperature, and the polymer has high thermal stability and excellent processability. The dihalide can be a chloride, a bromide or an iodide, which has universal applicability to raw materials. The present invention achieves CO2 fixation by multi-component tandem polymerization while also preparing a fused ring polymer, and the fused ring polymer can be applied to the field of fluorescent probes.

[0074] The present invention adopts a dihalide with a specific structure, which has better stability, is not easy to decompose and deteriorate under normal conditions, has weak sensitivity to water and alcohol, etc., and does not require a too strict anhydrous and oxygen-free environment during storage and use; the dihalide also has higher reactivity. Compared with the defects of ordinary diacyl chlorides having more side reactions and low product selectivity, the dihalide has moderate reactivity, achieves higher reaction selectivity, and has a higher yield of the target product. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0076] Figure 1 is the thermogravimetric diagram of the condensed heterocyclic polymer P1 in Example 1 of the present invention;

[0077] Figure 2 is a differential scanning calorimeter of the condensed heterocyclic polymer P1 in Example 1 of the present invention;

[0078] Figure 3is a spectrum of the condensed heterocyclic polymer P1 in a mixed solvent according to Example 1 of the present invention;

[0079] Figure 4 is a schematic diagram of the results of the interaction between the polymer P1 of Example 1 of the present invention and metal ions in a mixed solvent;

[0080] Figure 5 The polymer of Example 1 of the present invention reacts with different concentrations of Ag + The test results of ion quenching reaction are shown in the figure on the left. The left figure shows the effect of polymer P1 on different concentrations of Ag. + The right figure shows the fluorescence intensity response diagram of the relative PL intensity (I0 / I) at 512nm and Ag + Linear relationship graph of concentration;

[0081] Figure 6 is the hydrogen spectrum of the fused heterocyclic polymer P3, monomer 1b, and monomer 2a of Example 3 of the present invention;

[0082] Figure 7 It is the carbon spectrum of the fused heterocyclic polymer P3, monomer 1b and monomer 2a of Example 3 of the present invention. DETAILED DESCRIPTION

[0083] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0084] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0085] Example 1

[0086] This embodiment provides a method for preparing polyoxazolidinone, comprising the following steps:

[0087] (1) The terminal alkyne compound 1a has the following structural formula, and its preparation method is referred to the document Polym. Chem., 2017, 8, 2713-2722. The dihalide 2a is 1,6-dibromohexane (commercially available, purchased from Anaiji Chemical).

[0088]

[0089] Add magnetron, monomer 1a (76 mg, 0.2 mmol) and Ph3P (10.48 mg, 0.04 mmol) to a 25 mL dry schlenk reaction tube, then add CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) in an argon-protected glove box, take the polymerizer tube sealed with a rubber stopper out of the glove box, evacuate (30 min), change nitrogen (1 min) once, evacuate again, inject dry DMF (1 mL) into the tube with a syringe, evacuate again, insert a needle into a CO2 balloon, and inject 2a (30.77 μl, 0.2 mmol) into the tube with a microinjector. Place the polymerizer tube in a 60°C heated metal block and stir for 24 h (speed of 400 r / min), and after the reaction is completed and cooled to room temperature, an intermediate product is obtained.

[0090] (2) Dissolve NHPI (the molar ratio of NHPI to monomer 1a is 6:1) in ultra-dry DMF (1 mL), inject into the system with a syringe, and react at room temperature for 3 h. After the reaction, a crude product reaction solution is obtained. The reaction solution is diluted to 5 ml with dichloromethane to obtain a polymer solution; under stirring at a speed of 600 r / min, the 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 a fused heterocyclic polymer P1, whose structural formula is as follows.

[0091]

[0092] The yield of the condensed heterocyclic polymer P1 was determined to be 65%, the weight average molecular weight was 20,500, and the molecular weight distribution was 1.55. The condensed heterocyclic polymer P1 was dispersed in the DMF solvent and aggregated in the DMF aqueous solution (the volume ratio of water to DMF was 1:1). The concentration of P1 in the DMF aqueous solution was 10 -5 M, and showed good fluorescence emission, and thus it was inferred that the fused heterocyclic polymer could be applied in the field of luminescence. In addition, the fused heterocyclic polymer P1 was easily soluble in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF, DMSO, etc. at room temperature, indicating excellent solubility and processability. Figure 1 The thermal weight loss diagram of P1, the thermal decomposition temperature (thermal decomposition temperature refers to the temperature corresponding to 5% weight loss) is 226℃, Figure 2 This is the differential scanning calorimeter of P1. The glass transition temperature is 148°C, indicating that the prepared fused heterocyclic polymer P1 has good thermal stability.

[0093] Figure 3 The left side shows the spectrum of polymer P1 in a mixed solvent (mixed solvent includes water and DMF in different volume ratios). w It represents the volume percentage of water in the mixed solvent. Figure 3The right side shows the relationship between the relative intensity of PL (I / I0) in the mixed solvent (the mixed solvent 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 hardly emits light in pure DMF solution. When 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 mixed solvent with a concentration of 50%, the maximum fluorescence intensity of polymer P1 is 35.1 times that of polymer P1 in pure DMF solution. This proves that polymer P1 containing tetraphenylethylene (TPE) groups exhibits typical aggregation-induced emission (AIE) characteristics.

[0094] Figure 4 This is a schematic diagram of the interaction between polymer P1 and metal ions in a mixed solvent. Figure 4 Figure a shows the relative PL intensity (I0 / I) of polymer P1 after 120 min of interaction with different metal ions in a mixed solvent (DMF and water volume ratio is 1:1). 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 surprisingly found that 22 metal cations, including Fe 3+ There was no significant change in the fluorescence of the 22 ions, but after 2 hours of observation, Ag + Ions gradually darken the color of the probe solution under sunlight (see Figure 4 b), the fluorescence of the probe is weakened under ultraviolet light ( Figure 4 (c in Figure ).

[0095] In addition, in order to study the effect of the polymer on Ag +The sensitivity of the ion quenching reaction was investigated by titration experiments of silver ions on the fused heterocyclic polymer P1. + The test results of ion quenching reaction are shown in Figure 5 . Figure 5 The left figure shows the effect of polymer P1 on different concentrations of Ag + The right figure shows the fluorescence intensity response diagram of the relative PL intensity (I0 / I) at 512nm and Ag + The linear relationship diagram of the concentration. + Relative PL intensity (I0 / I) after ion interaction with polymer probe for 120 minutes, with Ag as the + The ion concentration is the horizontal axis, and the relative PL intensity (I0 / I) is the vertical axis. The resulting curve is shown in Figure 5 In the right figure, the relative PL intensity (I0 / I) and [Ag + The Stern-Volmer curve of ] shows a good linear relationship, and the quenching constant is calculated to be 2980M -1 , LOD is 4.90×10 -6 M, indicating that the fused heterocyclic polymer can perform trace qualitative detection of silver ions.

[0096] Example 2

[0097] This embodiment provides a method for preparing a fused heterocyclic polymer, comprising the following steps:

[0098] (1) The terminal alkyne compound 1a is the same as in Example 1. The dihalide 2b is 1,4-dichlorobenzyl (commercially available from Anaiji Chemical).

[0099] Add magnetron, monomer 1a (76 mg, 0.2 mmol), Ph3P (10.48 mg, 0.04 mmol) and 2b (35.01 mg, 0.2 mmol) to a 25 mL dry schlenk reaction tube, then add CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) in an argon-protected glove box, take the polymer tube sealed with a rubber stopper out of the glove box, evacuate (30 min), change nitrogen (1 min) once, evacuate again, inject dry DMF (1 mL) into the tube with a syringe, evacuate again, and insert a CO2 balloon with a needle. Place the polymer tube in a 60 ° C heating metal block and stir the reaction for 24 h (speed of 400 r / min), and after the reaction is cooled to room temperature, an intermediate product is obtained.

[0100] (2) Dissolve NHPI (the molar ratio of NHPI to monomer 1a is 6:1) in ultra-dry DMF (1 mL), inject into the system with a syringe, and react at room temperature for 3 h. After the reaction, a crude product reaction solution is obtained. The reaction solution is diluted to 5 mL with dichloromethane to obtain a polymer solution. The polymer solution is added dropwise to methanol under stirring at a speed of 600 r / min, and then allowed to stand for 4 h, filtered, and dried under vacuum at 50° C. to constant weight to obtain a fused heterocyclic polymer P2, the structural formula of which is as follows.

[0101]

[0102] The yield of the fused heterocyclic polymer P2 was determined to be 82%, the weight average molecular weight was 39,800, and the molecular weight distribution was 2.30. P2 showed good fluorescence emission in both DMF solvent and DMF aqueous solution (water to DMF volume ratio 7:3) (concentration 10 - 5 M). In addition, the fused heterocyclic polymer is easily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0103] Example 3

[0104] This embodiment provides a method for preparing a fused heterocyclic polymer, comprising the following steps:

[0105] (1) The terminal alkyne compound 1b has the following structural formula and is synthesized in the same manner as in Example 1. The dihalide is the same as in Example 1.

[0106]

[0107] Add magnetron, monomer 1b (58.66 mg, 0.2 mmol) and Ph3P (10.48 mg, 0.04 mmol) to a 25 mL dry schlenk reaction tube, then add CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) in an argon-protected glove box, take the polymerization tube sealed with a rubber stopper out of the glove box, evacuate (30 min), change nitrogen (1 min) once, evacuate again, inject dry DMF (1 ml) into the tube with a syringe, evacuate again, insert a needle into a CO2 balloon, and inject 2a (30.77 μl, 0.2 mmol) into the tube with a microinjector. Place the polymerization tube in a 60°C heated metal block and stir for 24 h (speed of 400 r / min), and the reaction is cooled to room temperature to obtain an intermediate product.

[0108] (2) Dissolve NHPI (the molar ratio of NHPI to monomer 1b is 6:1) in ultra-dry DMF (1 mL), inject into the system with a syringe, and react at room temperature for 3 h. After the reaction, a crude product reaction solution is obtained. The reaction solution is diluted to 5 mL with dichloromethane to obtain a polymer solution. The polymer solution is added dropwise to methanol under stirring at a speed of 600 r / min, and then allowed to stand for 4 h, filtered, and dried under vacuum at 50° C. to constant weight to obtain a fused heterocyclic polymer P3, the structural formula of which is as follows.

[0109]

[0110] It was determined that the yield of the fused heterocyclic polymer P3 was 76%, the weight average molecular weight was 23,500, and the molecular weight distribution was 1.71. Figure 6 The hydrogen spectra of fused heterocyclic polymer P3, monomer 1b and monomer 2a; wherein A is the hydrogen spectrum of monomer 1b, B is the hydrogen spectrum of monomer 2a, C is the hydrogen spectrum of NHPI, D is the hydrogen spectrum of the model compound, the structural formula of the model compound is as follows, the preparation method refers to the literature Green Chem., 2015, 17, 4061-4067, and E is the hydrogen spectrum of fused heterocyclic polymer P3. Figure 7 These are the carbon spectra of fused heterocyclic polymer P3, monomer 1b, and monomer 2a; wherein A is the carbon spectrum of monomer 1b, B is the carbon spectrum of monomer 2a, C is the carbon spectrum of NHPI, D is the carbon spectrum of the model compound, and E is the carbon spectrum of the fused heterocyclic polymer P3.

[0111]

[0112] from Figure 6 The structure of the fused heterocyclic polymer P3 can be determined. 1 The H NMR peak of alkyne hydrogen is at δ4.02. Figure 6 C) and polymer P3( Figure 6 In the spectrum of E), the NMR peaks of the alkyne hydrogen disappeared, while the characteristic NMR peak of the methylene hydrogen near the ester group appeared at δ4.09. Figure 7 It can be seen that monomer 1b ( Figure 7 The NMR peaks representing the triple bond carbon in A) are retained in polymer P3, but in the model compound ( Figure 7 C) and polymer P3( Figure 7 This is due to the introduction of NHPI ( Figure 7 D) reacts with the carbon-carbon triple bond to form an isoxazole isoindole structure. 13In the C NMR spectrum, not only the carbonyl carbon and the methylene carbon near the ester group that did not react with NHPI were retained, the corresponding NMR peaks appeared at δ161.33 and δ64.40 respectively. In addition, the NMR peak of the carbonyl carbon in the newly formed isoindole ring appeared at δ167.70. This shows that the polymerization reaction has been successfully carried out and has an excellent post-modification grafting rate.

[0113] Example 4

[0114] This embodiment provides a method for preparing a fused heterocyclic polymer, comprising the following steps:

[0115] (1) The terminal alkyne compound 1b is the same as in Example 3. The dihalide 2b is 1,4-p-dichlorobenzene (commercially available from Anaiji Chemical).

[0116] Add magnetron, monomer 1b (58.66 mg, 0.2 mmol), Ph3P (10.48 mg, 0.04 mmol) and 2b (35.01 mg, 0.2 mmol) to a 25 mL dry schlenk reaction tube, then add CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) in an argon-protected glove box, take the polymer tube sealed with a rubber stopper out of the glove box, evacuate (30 min), change nitrogen (1 min) once, evacuate again, inject dry DMF (1 mL) into the tube with a syringe, evacuate again, and insert a CO2 balloon with a needle. Place the polymer tube in a 60 ° C heating metal block and stir the reaction for 24 h (speed of 400 r / min), and the reaction is cooled to room temperature to obtain the intermediate product.

[0117] (2) Dissolve NHPI (the molar ratio of NHPI to monomer 1b is 6:1) in ultra-dry DMF (1 mL), inject into the system with a syringe, and react at room temperature for 3 h. After the reaction, a crude product reaction solution is obtained. The reaction solution is diluted to 5 mL with dichloromethane to obtain a polymer solution; under stirring at a speed of 600 r / min, the polymer solution is added dropwise to methanol, then allowed to stand for 4 h, filtered, and dried under vacuum at 50°C to constant weight to obtain a fused heterocyclic polymer P4, the structural formula of which is as follows.

[0118]

[0119] The yield of the condensed heterocyclic polymer P4 was determined to be 80%, the weight average molecular weight was 33,200, and the molecular weight distribution was 2.21. The condensed heterocyclic polymer P4 was easily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0120] Example 5

[0121] This embodiment provides a method for preparing a fused heterocyclic polymer, comprising the following steps:

[0122] (1) Terminal alkyne compound 1c, the synthesis method is the same as that of Example 1, the structural formula is as follows, the terminal alkyne compound is a white solid, and the yield is 82%. Dihalide 2a is 1,6-dibromohexane (commercially available, purchased from Anaiji Chemical).

[0123]

[0124] Add magnetron, monomer 1c (90.4 mg, 0.2 mmol) and Ph3P (10.48 mg, 0.04 mmol) to a 25 mL dry schlenk reaction tube, then add CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) in an argon-protected glove box, take the polymerization tube sealed with a rubber stopper out of the glove box, evacuate (30 min), change nitrogen (1 min) once, evacuate again, inject dry DMF (1 mL) into the tube with a syringe, evacuate again, insert a needle into a CO2 balloon, and inject 2a (30.77 μl, 0.2 mmol) into the tube with a microinjector. Place the polymerization tube in a 60°C heated metal block and stir for 24 h (speed of 400 r / min), and cool the reaction to room temperature to obtain the intermediate product.

[0125] (2) Use ultra-dry DMF (1 mL) to dissolve NHPI (the molar ratio of NHPI to monomer 1c is 6:1), inject it into the system with a syringe, and react at room temperature for 3 hours. After the reaction, a crude product reaction solution is obtained. The reaction solution is diluted to 5 mL with dichloromethane to obtain a polymer solution. Under stirring conditions at a speed of 600 r / min, the polymer solution is added dropwise to methanol, then allowed to stand for 4 hours, filtered, and vacuum dried at 50°C to constant weight to obtain a fused heterocyclic polymer P5 with the following structural formula.

[0126]

[0127] The yield of the fused heterocyclic polymer P5 was determined to be 75%, the weight average molecular weight was 28,000, and the molecular weight distribution was 1.93. P5 was easily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0128] Example 6

[0129] This embodiment provides a method for preparing a fused heterocyclic polymer, comprising the following steps:

[0130] (1) The terminal alkyne compound 1c is the same as in Example 5. The dihalide 2b is 1,4-dichlorobenzyl (commercially available from Anaiji Chemical).

[0131] Add magnetron, monomer 1c (90.4 mg, 0.2 mmol), Ph3P (10.48 mg, 0.04 mmol) and 2b (35.01 mg, 0.2 mmol) to a 25 mL dry schlenk reaction tube, then add CuCl (3.98 mg, 0.04 mmol) and Cs2CO3 (456 mg, 1.4 mmol) in an argon-protected glove box, take the polymer tube sealed with a rubber stopper out of the glove box, evacuate (30 min), replace nitrogen (1 min) once, evacuate again, inject dry DMF (1 mL) into the tube with a syringe, evacuate again, and insert a CO2 balloon with a needle. Place the polymer tube in a 60 ° C heating metal block and stir for 24 h (speed of 400 r / min), and after the reaction is cooled to room temperature, an intermediate product is obtained.

[0132] (2) Use ultra-dry DMF (1 mL) to dissolve NHPI (the molar ratio of NHPI to monomer 1c is 6:1), inject it into the system with a syringe, and react at room temperature for 3 hours. After the reaction, a crude product reaction solution is obtained. The reaction solution is diluted to 5 mL with dichloromethane to obtain a polymer solution; under stirring conditions at a speed of 600 r / min, the polymer solution is added dropwise to methanol, then allowed to stand for 4 hours, filtered, and vacuum dried at 50°C to constant weight to obtain a fused heterocyclic polymer P6, the structural formula of which is as follows.

[0133]

[0134] The yield of the fused heterocyclic polymer P6 was determined to be 85.5%, the weight average molecular weight was 42,700, and the molecular weight distribution was 2.68. P6 was easily soluble in common organic solvents such as DMF and DMSO at room temperature, indicating excellent solubility and processability.

[0135] Obviously, the above embodiments are merely examples for clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from them are still within the protection scope of the invention.

Claims

1. A fused heterocyclic polymer, characterized in that: Has any of the following structural formulas: Wherein, n is 10 to 500; R 1 , R 1’ , R 1” , R 2 Each of the following is independently selected from one of an aromatic group and an aliphatic group.

2. The fused heterocyclic polymer according to claim 1, characterized in that Satisfy at least one of (1) to (5): (1) R 1 Select one of the following structural formulas: The m is 1 to 20, h is 1 to 20, j is 1 to 20, k is 1 to 20, and l is 1 to 20; the Y is selected from at least one of NH, O or S; * indicates the substitution position; (2) R 1’ Select one of the following structural formulas: * indicates a replacement position; (3) R 1” Select one of the following structural formulas: * indicates a replacement position; (4) R 2 Select one of the following structural formulas: The o is 1 to 20, the p is 1 to 20; * indicates the substitution position; (5) R 3 At least one selected from 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 a CO2-containing atmosphere, a terminal alkyne compound and a dihalide undergo a polymerization reaction to obtain an intermediate product; (2) Adding N-hydroxyphthalimide and its derivatives 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 Select one of the following structural formulas: Preferably, the R 1’ Select one of the following structural formulas: Preferably, the R 1” Select one of the following structural formulas: The m is 1 to 20, h is 1 to 20, j is 1 to 20, k is 1 to 20, and l is 1 to 20; the 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, said X comprises bromine, chlorine or iodine; Preferably, the R 2 Select one of the following structural formulas: The oo is 1 to 20, the p is 1 to 20, and * indicates a 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 the 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 to 1.2):(0.8 to 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 the step (1), the polymerization reaction temperature is from room temperature to 100° C. and the reaction time is from 6 to 24 hours; and / or, In step (2), the polymerization reaction temperature is room temperature to 80° C., and the reaction time is 1 to 10 hours; and / or, In the step (1), the polymerization reaction temperature is room temperature to 60° C. and the reaction time is 22 to 24 hours; and / or, In the step (2), the polymerization reaction temperature is room temperature to 60° C., and the reaction time is 2 to 4 hours.

8. The preparation method according to claim 4, characterized in that: The step (1) further comprises adding at least one of a solvent and a catalyst before carrying out the polymerization reaction; Preferably, the solvent comprises at least one of 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 a base catalyst; Preferably, the copper catalyst comprises at least one of cuprous iodide, cuprous bromide, cuprous chloride, cuprous acetate and cuprous sulfate; Preferably, the base catalyst includes 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.

9. The preparation method according to claim 8, characterized in that: The catalyst comprises 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 base 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 to 0.5 mol / L.

10. Use 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 to detect Ag + ; Preferably, the fused heterocyclic polymer is used as a fluorescent material.

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