Electroluminescent organic polymer material and preparation method and application thereof

Abstract

The application belongs to the technical field of electrochemiluminescence materials, and particularly relates to an electroluminescent organic polymer material and a preparation method and application thereof, and the preparation method comprises the following steps: 1) dissolving meso-tetra(4-carboxyphenyl) porphyrin and a zinc salt in a solvent to obtain a mixed system, stirring and reacting, centrifuging, and drying to obtain a zinc porphyrin ligand; 2) adding tetra-(4-aminophenyl) ethylene, dichlorosulfoxide and mesitylene into the synthesized zinc porphyrin ligand respectively, stirring uniformly to obtain a secondary mixed system; 3) adding polyvinylpyrrolidone into the secondary mixed system, and heating and refluxing at 70-80 DEG C for 20-25 h; and 4) centrifuging and washing after reaction, and drying to obtain the product. Compared with Zn-Tccp-Tpe polymer and PVP-Tccp-Tpe polymer, the PVP-Zn-Tccp-Tpe organic polymer has stronger electrochemiluminescence signals and more stable luminescent performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrochemiluminescence (ECL) materials, in particular to an electrochemiluminescence organic polymer material and a preparation method and application thereof. BACKGROUND

[0002] The electrochemiluminescence process is a radiation process, which refers to that a high active free radical generated near the working electrode participates in the electron transfer process, and then forms an excited state, and when returning to the ground state, the excess energy is released in the form of light. Since it does not need an additional light source, it can effectively reduce the influence of background signal, and has a wide detection range, and thus has attracted widespread attention.

[0003] Due to the unique molecular structure and electronic properties of porphyrin derivatives, these compounds usually have a large planar structure, good electron transport capacity and light absorption properties. At the same time, in terms of electrochemiluminescence, porphyrin derivatives can change the luminescence color or improve the luminescence efficiency by changing their structure, such as changing their substituents, bridging groups or core coordination metal ions; at the same time, porphyrin derivatives usually have high electrode transmission efficiency, and by coordinating different metal ions at the porphyrin center, the electron conduction rate can be further improved, which makes it more conducive to the transmission of electrons from the cathode to the luminescent layer and thus improves the luminescence efficiency; finally, compared with other organic matters, porphyrin widely exists in the bodies of animals and plants in nature, and is an environmentally friendly substance, and by designing and synthesizing porphyrin derivatives with good stability, the service life and stability of the sensor can be effectively improved. However, porphyrin and its derivatives will form an aggregate state in aqueous solution or solid, which will cause the emission to be quenched, which is still a great challenge faced by porphyrin and its derivatives.

[0004] Tetrakis-(4-aminophenyl)ethylene (Tpe) is a compound with unique optical properties, which usually does not emit light in solution, but can emit strong fluorescence in aggregate state, which is called aggregation-induced emission (AIE). SUMMARY

[0005] The present application provides an electrochemiluminescence organic polymer material and a preparation method and application thereof, which solves the problem of poor luminescence of meso-tetrakis(4-carboxyphenyl) porphyrin (Tccp) due to the induced aggregation quenching phenomenon; at the same time, the condensation of Tpe and Tccp significantly improves the luminescence performance compared with the use of Tccp alone, and the successful coordination of zinc ions further improves the conductivity of the polymer and enhances its luminescence performance.

[0006] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0007] A preparation method of an electroluminescent organic polymer material, comprising the following steps:

[0008] (1) dissolving equimolar meso-tetra(4-carboxyphenyl) porphyrin (Tccp) and zinc salt in a solvent to obtain a mixed system, stirring the reaction at room temperature, centrifuging, and drying to obtain a zinc porphyrin (Zn-Tccp) ligand;

[0009] (2) adding tetra-(4-aminophenyl) ethylene (Tpe) and dichlorosulfoxide into the Zn-Tccp ligand synthesized in step (1) respectively, stirring uniformly to obtain a secondary mixed system;

[0010] (3) adding polyvinylpyrrolidone (PVP) into the secondary mixed system obtained in step (2), heating and refluxing the reaction at 70-80°C for 20-25h;

[0011] (4) centrifuging and washing the solution obtained after the reaction, and drying to obtain the electroluminescent organic polymer material (PVP-Zn-Tccp-Tpe).

[0012] Preferably, the zinc salt in step (1) is one or more of zinc acetate, zinc nitrate, zinc sulfate or zinc chloride, and the solvent is anhydrous ethanol or methanol.

[0013] Preferably, the concentration of the meso-tetra(4-carboxyphenyl) porphyrin and the zinc salt in step (1) is 0.5-2.0nmol / mL.

[0014] Preferably, the stirring time in step (1) is 2-6h, and the centrifuging condition is a rotation speed of 6000-10000rpm for 5-15min.

[0015] Preferably, the mass ratio of the tetra-(4-aminophenyl) ethylene to the meso-tetra(4-carboxyphenyl) porphyrin is 1:1, and the dosage ratio of the dichlorosulfoxide to the meso-tetra(4-carboxyphenyl) porphyrin is 3mL:2mg.

[0016] Preferably, the preparation method further comprises adding mesitylene in step (2), and the dosage ratio of the mesitylene to the dichlorosulfoxide is 1:1.

[0017] Preferably, the concentration of the Zn-Tccp in the secondary mixed system in step (2) is 0.2-0.6nmol / mL, and the concentration of the tetra-(4-aminophenyl) ethylene is 0.4-1.2nmol / mL.

[0018] Preferably, the mass ratio of the polyvinylpyrrolidone to the meso-tetra(4-carboxyphenyl) porphyrin in step (3) is 5:1.

[0019] The application also provides an electroluminescent organic polymer material prepared by the method.

[0020] In addition, the application also provides an application of the electroluminescent organic polymer material prepared by the preparation method in an electrochemiluminescence sensor.

[0021] By adopting the technical scheme, the application has the following beneficial effects:

[0022] The PVP-Zn-Tccp-Tpe electroluminescent organic polymer material solves the problem of poor luminescence caused by the aggregation-induced quenching phenomenon of Tccp; meanwhile, the condensation of Tpe and Tccp significantly improves the luminescent performance of Tccp, the successful coordination of zinc ions further improves the conductivity of the polymer and enhances the luminescent performance. In addition, the dichlorosulfoxide as a solvent can also react with the carboxyl group of the zinc porphyrin ligand to produce an acyl chloride group, and the acyl chloride group is more easily reacted with the amino group of the tetraphenylethylene, so that the two ligands of zinc porphyrin and tetraphenylethylene are effectively connected; mesitylene can adjust the lattice spacing and reduce the aggregation degree of the material, thereby further improving the luminescent intensity. Therefore, the PVP-Zn-Tccp-Tpe electroluminescent organic polymer material has a significantly improved electrochemiluminescent intensity compared with its ligands (Tccp, Tpe and Zn-Tccp). Moreover, the organic polymer (PVP-Zn-Tccp-Tpe) has a stronger and more excellent electrochemiluminescent signal and more stable luminescent performance compared with the Zn-Tccp-Tpe polymer material and the PVP-Tccp-Tpe polymer material. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 The synthesis path of the electroluminescent organic polymer material of the embodiment of the application is shown.

[0024] Figure 2 The SEM images of the materials obtained in Example 1 and Comparative Example 1 are shown, wherein the SEM images of the material obtained in Comparative Example 1 at 200 nm and 100 nm are A and B, and the SEM images of the material obtained in Example 1 at 1 μm and 300 nm are C and D.

[0025] Figure 3 The XRD images of the three organic polymer materials of Zn-Tccp-Tpe, PVP-Tccp-Tpe and PVP-Zn-Tccp-Tpe are shown.

[0026] Figure 4 The ultraviolet absorption graph of the electroluminescent organic polymer material obtained in Example 1 is shown.

[0027] Figure 5 The Fourier transform infrared spectrogram of the electroluminescent organic polymer material obtained in Example 1 of the present application.

[0028] Figure 6 The X-ray photoelectron spectrometer analysis spectrogram of the electroluminescent organic polymer material obtained in Example 1 of the present application.

[0029] Figure 7 The ECL emission wavelength spectrogram of the electroluminescent organic polymer material obtained in Example 1 of the present application.

[0030] Figure 8 The ECL signal comparison chart of the electroluminescent organic polymer materials obtained in Example 1, Comparative Example 1 and Comparative Example 2 of the present application under the same conditions.

[0031] Figure 9 The ECL signal comparison chart of Example 1 and each ligand of the present application.

[0032] Figure 10 The CV response comparison chart of Example 1 and each ligand of the present application.

[0033] Figure 11 The CV response comparison chart of the electroluminescent organic polymer materials obtained in Example 1, Comparative Example 1 and Comparative Example 2 of the present application. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the present application.

[0035] Example 1

[0036] A preparation method of an electroluminescent organic polymer material (PVP-Zn-Tccp-Tpe) comprises the following steps:

[0037] (1) 10 mg of meso-tetra(4-carboxyphenyl) porphyrin (Tccp) and 3 mg of zinc acetate are dissolved in anhydrous ethanol solvent in a round-bottom flask to obtain a mixed system with the concentration of Tccp and zinc acetate both being 0.83 nmol / mL, which is stirred at room temperature for 4 hours, centrifuged under the condition of a rotation speed of 10,000 rpm and a time of 5 min, and dried at 37℃ to obtain a zinc porphyrin Zn-Tccp ligand;

[0038] (2) In the Zn-Tccp ligand synthesized in step (1), 10 mg of tetra-(4- aminophenyl) ethylene (Tpe), 15 mL of dichlorosulfoxide and 15 mL of 1,3,5- trimethylbenzene were added respectively, and stirred uniformly to obtain a secondary mixed system with a Zn-Tccp concentration of 0.415 nmol / mL and a Tpe concentration of 0.83 nmol / mL;

[0039] (3) 50 mg of polyvinylpyrrolidone (PVP) was added to the secondary mixed system obtained in step (2), and heated to reflux at 78°C for 24 h;

[0040] (4) The solution obtained after the reaction was centrifuged and washed, the centrifugation condition was 10000 rpm for 5 min, the washing reagent was tetrahydrofuran and methanol, and the two reagents were washed alternately for a total of six times, and then dried under vacuum at 37°C to obtain the electroluminescent organic polymer material (PVP-Zn-Tccp-Tpe).

[0041] Example 2

[0042] A preparation method of an electroluminescent organic polymer material (PVP-Zn-Tccp-Tpe) comprises the following steps:

[0043] (1) 10 mg of meso-tetra(4-carboxyphenyl) porphyrin (Tccp) and 3 mg of zinc nitrate were dissolved in methanol solvent in a round-bottom flask to obtain a mixed system with a Tccp and zinc acetate concentration of 0.12 nmol / mL, which was stirred at room temperature for 4 h, centrifuged at a speed of 10000 rpm for 5 min, and dried at 37°C to obtain a zinc porphyrin Zn-Tccp ligand;

[0044] (2) In the Zn-Tccp ligand synthesized in step (1), 10 mg of tetra-(4- aminophenyl) ethylene (Tpe), 15 mL of dichlorosulfoxide and 15 mL of 1,3,5- trimethylbenzene were added respectively, and stirred uniformly to obtain a secondary mixed system with a Zn-Tccp concentration of 0.415 nmol / mL and a Tpe concentration of 0.83 nmol / mL;

[0045] (3) 50 mg of polyvinylpyrrolidone (PVP) was added to the secondary mixed system obtained in step (2), and heated to reflux at 80°C for 24 h;

[0046] (4) The solution obtained after the reaction was centrifuged and washed, the centrifugation condition was 10000 rpm for 5 min, the washing reagent was tetrahydrofuran and methanol, and the two reagents were washed alternately for a total of six times, and then dried under vacuum at 37°C to obtain the electroluminescent organic polymer material (PVP-Zn-Tccp-Tpe).

[0047] Comparative Example 1

[0048] A preparation method of an electroluminescent organic polymer material (Zn-Tccp-Tpe) comprises the following steps:

[0049] (1) 10 mg of meso-tetra(4-carboxyphenyl)porphyrin (Tccp) and 3 mg of zinc acetate are dissolved in anhydrous ethanol solvent to obtain a mixed system with a Tccp concentration and a zinc acetate concentration of 0.83 nmol / mL, stirring at room temperature for 4 hours, centrifuging at a speed of 10,000 rpm for 5 min, and drying at 37°C to obtain a zinc porphyrin Zn-Tccp ligand;

[0050] (2) 10 mg of tetra-(4-aminophenyl)ethylene (Tpe), 15 mL of dichlorosulfoxide, and 15 mL of 1,3,5-trimethylbenzene are added to the Zn-Tccp ligand synthesized in step (1), and stirred uniformly to obtain a secondary mixed system with a Zn-Tccp concentration of 0.415 nmol / mL and a Tpe concentration of 0.83 nmol / mL; heating and refluxing at 78°C for 24 h;

[0051] (3) The solution obtained after the reaction is centrifuged and washed, the centrifugation condition is a speed of 10,000 rpm for 5 min, the washing reagents are tetrahydrofuran and methanol, the two reagents are washed alternately, a total of six times, and then vacuum dried at 37°C to obtain the electroluminescent organic polymer material (Zn-Tccp-Tpe).

[0052] Comparative Example 2

[0053] A preparation method of an electroluminescent organic polymer material (PVP-Tccp-Tpe) comprises the following steps:

[0054] (1) 10 mg of tetra-(4-aminophenyl)ethylene (Tpe), 15 mL of dichlorosulfoxide, and 15 mL of 1,3,5-trimethylbenzene are added to the Tccp ligand, and stirred uniformly to obtain a mixed system with a Zn-Tccp concentration of 0.415 nmol / mL and a Tpe concentration of 0.83 nmol / mL;

[0055] (2) 50 mg of polyvinylpyrrolidone (PVP) is added to the mixed system obtained in step (1), and heated and refluxed at 78°C for 24 h;

[0056] (3) The solution obtained after the reaction is centrifuged and washed, the centrifugation condition is a speed of 10,000 rpm for 5 min, the washing reagents are tetrahydrofuran and methanol, the two reagents are washed alternately, a total of six times, and then vacuum dried at 37°C to obtain the electroluminescent organic polymer material (PVP-Tccp-Tpe).

[0057] The electrochemiluminescence organic polymer material obtained in Example 1, Comparative Example 1 and Comparative Example 2 was characterized by SEM and XRD, and the results are shown in Figs. 1-3, respectively. Figure 2 Figure 2 The SEM characterization of A, B in Fig. 1 shows that the organic polymer material (Zn-Tccp-Tpe) obtained in Comparative Example 1 has a lamellar stacking structure, but the flaky particles are larger. Figure 2 The SEM characterization of C, D in Fig. 2 shows that after the addition of PVP, the flaky particle diameter of the organic polymer material (PVP-Zn-Tccp-Tpe) obtained in Example 1 is smaller than that of the organic polymer material of Comparative Example 1.

[0058] The XRD characterization of Fig. 3 shows that the organic polymer material (PVP-Zn-Tccp-Tpe) obtained in Example 1 has a distinct characteristic peak at 0.98°. The organic polymer material (Zn-Tccp-Tpe) obtained in Comparative Example 1 has a distinct characteristic peak at 1.14°. The organic polymer material (PVP-Tccp-Tpe) obtained in Comparative Example 2 has a distinct peak at 0.96°. Figure 3 The present application also characterized the electrochemiluminescence organic polymer material obtained in Example 1 by UV-Vis, FT-IR, XPS and ECL test, and the results are shown in Figs. 4-6.

[0059] Figures 4 to 7

[0060] The characterization by UV-Vis spectrophotometer shows that the absorption wavelength of the organic polymer material obtained in Example 1 is 273 nm. Figure 4 The characterization by FT-IR shows that the vibration peak of C=O bond at 1700 cm-1 and the vibration peak of C-O bond at 3356 cm-1 are observed for Tccp, indicating that Tccp has -COOH on the surface. The vibration peak of N-H bond at 1520 cm-1, 1620 cm-1 and 3360 cm-1 is observed for Tpe, indicating that Tpe has -NH2 on the surface. The broad and strong absorption peak at 3090 cm-1-3680 cm-1 in the infrared test of PVP is the stretching vibration of C-N bond, and the peak at 1670 cm-1 is the stretching vibration of C=O. The infrared spectrum of PVP-Zn-Tccp-Tpe only retains the peak at 1670 cm-1 compared with Tccp and Tpe, but this peak may also be the vibration peak generated by PVP, so this peak may be the amide bond formed by the condensation of Tccp and Tpe, or it may be the vibration peak generated by the carbonyl group on PVP.

[0061] Figure 5 The characterization by FT-IR shows that the vibration peak of C=O bond at 1700 cm-1 and the vibration peak of C-O bond at 3356 cm-1 are observed for Tccp, indicating that Tccp has -COOH on the surface. The vibration peak of N-H bond at 1520 cm-1, 1620 cm-1 and 3360 cm-1 is observed for Tpe, indicating that Tpe has -NH2 on the surface. The broad and strong absorption peak at 3090 cm-1-3680 cm-1 in the infrared test of PVP is the stretching vibration of C-N bond, and the peak at 1670 cm-1 is the stretching vibration of C=O. The infrared spectrum of PVP-Zn-Tccp-Tpe only retains the peak at 1670 cm-1 compared with Tccp and Tpe, but this peak may also be the vibration peak generated by PVP, so this peak may be the amide bond formed by the condensation of Tccp and Tpe, or it may be the vibration peak generated by the carbonyl group on PVP.

[0062] The characterization by FT-IR shows that the vibration peak of C=O bond at 1700 cm-1 and the vibration peak of C-O bond at 3356 cm-1 are observed for Tccp, indicating that Tccp has -COOH on the surface. The vibration peak of N-H bond at 1520 cm-1, 1620 cm-1 and 3360 cm-1 is observed for Tpe, indicating that Tpe has -NH2 on the surface. The broad and strong absorption peak at 3090 cm-1-3680 cm-1 in the infrared test of PVP is the stretching vibration of C-N bond, and the peak at 1670 cm-1 is the stretching vibration of C=O. The infrared spectrum of PVP-Zn-Tccp-Tpe only retains the peak at 1670 cm-1 compared with Tccp and Tpe, but this peak may also be the vibration peak generated by PVP, so this peak may be the amide bond formed by the condensation of Tccp and Tpe, or it may be the vibration peak generated by the carbonyl group on PVP.​​​​Figure 6 It can be seen from the X-ray photoelectron spectroscopy (XPS) characterization that the C=C peak at 284.18 eV is obtained, the C-O peak at 531.68 eV and the C=O peak at 532.98 eV are obtained, and the -C=O peak at 288.08 eV is obtained, which is referred to the polymer structure formula in Figure 1 and the infrared spectrum of Figure 5 , and it is judged that the peak at 288.08 eV is generated due to the vibration of an amide bond, and the Zn-N peak at 1021.7 eV is obtained.

[0063] It can be seen from the X-ray photoelectron spectroscopy (XPS) characterization that the C=C peak at 284.18 eV is obtained, the C-O peak at 531.68 eV and the C=O peak at 532.98 eV are obtained, and the -C=O peak at 288.08 eV is obtained, which is referred to the polymer structure formula in Figure 7 , and the infrared spectrum of , and it is judged that the peak at 288.08 eV is generated due to the vibration of an amide bond, and the Zn-N peak at 1021.7 eV is obtained.

[0064] The application example 1 of the present application is applied to the electrochemiluminescence intensity of the organic polymer materials prepared from the example 1, the comparative example 1 and the comparative example 2, and the specific operation steps are as follows:

[0065] (1) A glassy carbon electrode is taken, polished and polished with aluminum powder, and then ultrasonically cleaned with distilled water and ethanol, and dried with nitrogen.

[0066] (2) 1 mg of the organic polymer of the example 1, the comparative example 1 and the comparative example 2 is taken respectively, and dispersed in 6 mL of 1% chitosan solution. 10 μL of the dispersion is dropped on the surface of the glassy carbon electrode, and left to dry at room temperature as a working electrode. 0.1M PBS (pH=7.4) containing 0.1M K2S2O8 is prepared as a co-reaction solvent. A saturated Ag / AgCl electrode is used as a reference electrode, and a platinum wire electrode is used as a counter electrode to construct a three-electrode system with the above-prepared working electrode. The three-electrode system is placed in the co-reaction solvent, and the ECL signal is tested by cyclic voltammetry.

[0067] The results are shown in

[0068] , the electrochemiluminescence signal of the organic polymer (PVP-Zn-Tccp-Tpe) of the example 1 is excellent and has good light stability; the electrochemiluminescence signal of the organic polymer (Zn-Tccp-Tpe) of the comparative example 1 is low and has poor stability; the electrochemiluminescence signal of the organic polymer (PVP-Tccp-Tpe) of the comparative example 2 has good stability, but is not as good as the organic polymer of the example 1 in signal intensity. Figure 8 The application example 2 of the present application is applied to the electrochemiluminescence intensity of the organic polymer materials prepared from the example 1, the comparative example 1 and the comparative example 2, and the specific operation steps are as follows:

[0069] The application example 2 of the present application is applied to the electrochemiluminescence intensity of the organic polymer materials prepared from the example 1, the comparative example 1 and the comparative example 2, and the specific operation steps are as follows:

[0070] The application example 2 takes the method of the application example 1 to prepare the working electrodes respectively with Tccp, Tpe, Zn-Tccp and PVP-Zn-Tccp-Tpe, takes the same method as the application example 1, respectively tests the ECL curves and CV curves of the working electrodes above and the working electrode in the experimental example 1, and the results are shown in Figure 9 、 10 .

[0071] From the ECL results of Figure 9 , it can be seen that the ECL intensity of the PVP-Zn-Tccp-Tpe of the example 1 is obviously improved compared with each ligand thereof.

[0072] From the CV results of Figure 10 , it can be seen that the reduction peak voltage of the organic polymer of the example 1 is left-shifted compared with the reduction peak voltage of each ligand thereof, which indicates that the organic polymer material is more easy to absorb electrons and more easy to occur reduction reaction, and then the electron is more easy to jump back to the ground state to occur light radiation, which corresponds to the ECL test result.

[0073] The application example 3

[0074] The application example 3 of the application takes the method of the application example 1 to prepare the working electrodes respectively with PVP-Tccp-Tpe, Zn-Tccp-Tpe and PVP-Zn-Tccp-Tpe, takes the same method as the application example 1, tests the CV curve signals of the working electrodes prepared by the above three organic polymer materials, and the results are shown in Figure 11 .

[0075] As shown in Figure 11 , in the CV test, the reduction potential of the PVP-Zn-Tccp-Tpe is the lowest, about-1.5V, which indicates that compared with the three materials, the PVP-Zn-Tccp-Tpe is more easy to occur reduction reaction, and thus the electrode is more easy to accept energy to enter into the excited state, which indicates from another aspect that the material has more excellent performance in the electro-luminescence performance compared with the other two materials. This result also corresponds to the ECL results of Figure 8 .

[0076] The above description is the detailed description of the preferable and feasible embodiments of the application, but the embodiments are not used to limit the patent application range of the application, and any equivalent change or modification completed under the technical spirit of the application should belong to the patent range covered by the application.

Claims

1. A method for preparing an electroluminescent organic polymer material, characterized in that: The steps include: (1) dissolving equal moles of meso-tetrakis(4-carboxyphenyl)porphine and zinc salt in a solvent to obtain a mixed system, stirring the mixture for reaction, centrifuging the mixture, and drying the mixture to obtain a zinc porphyrin ligand; the concentrations of meso-tetrakis(4-carboxyphenyl)porphine and zinc salt are both 0.5-2.0 nmol / mL; (2) Tetrakis-(4-aminophenyl)ethylene, thionyl chloride and mesitylene are added to the zinc porphyrin ligand synthesized in step (1) respectively, and stirred evenly to obtain a secondary mixed system; the mass ratio of the tetrakis-(4-aminophenyl)ethylene to mesitylene-(4-carboxyphenyl)porphine is 1:1, the amount ratio of the thionyl chloride to mesitylene-(4-carboxyphenyl)porphine is 3 mL:2 mg; the volume ratio of the mesitylene to thionyl chloride is 1:1; (3) adding polyvinyl pyrrolidone to the secondary mixed system obtained in step (2), and heating the mixture under reflux at 70-80°C for 20-25 hours; the mass ratio of the polyvinyl pyrrolidone to meso-tetrakis(4-carboxyphenyl)porphine is 5:1; (4) The solution obtained after the reaction is centrifuged, washed, and dried to obtain the electroluminescent organic polymer material.

2. The method for preparing an electroluminescent organic polymer material according to claim 1, wherein: The zinc salt in step (1) is one or more of zinc acetate, zinc nitrate, zinc sulfate or zinc chloride, and the solvent is anhydrous ethanol or methanol.

3. The method for preparing an electroluminescent organic polymer material according to claim 1, wherein: The stirring time in step (1) is 2-6 hours, and the centrifugal conditions are a rotation speed of 6000-10000 rpm and a time of 5-15 minutes.

4. The method for preparing an electroluminescent organic polymer material according to claim 1, wherein: The concentration of zinc porphyrin in the secondary mixing system of step (2) is 0.2-0.6 nmol / mL, and the concentration of tetrakis-(4-aminophenyl)ethylene is 0.4-1.2 nmol / mL.

5. An electroluminescent organic polymer material prepared according to the method according to any one of claims 1 to 4.

6. Use of the electroluminescent organic polymer material prepared by the preparation method according to any one of claims 1 to 4 in an electrochemiluminescence sensor.

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