A kind of polybenzodifuranone and its constant potential polymerization preparation method

Abstract

The application discloses a kind of polybenzodifuranone and its constant potential polymerization preparation method, belong to organic conductive polymer material preparation technical field, benzodifuranone (BFDO) and supporting electrolyte are dissolved in polar aprotic solvent, and electrolyte is obtained by mixing uniformly;With platinum metal electrode as working electrode and counter electrode, with saturated calomel electrode as reference electrode, three electrodes are connected with direct current power supply and are placed in the electrolyte, in air atmosphere, electrochemical polymerization reaction is carried out using constant potential method;After reaction, the reaction liquid is extracted and filtered, dried, to obtain polybenzodifuranone (PBFDO).The application uses constant potential electrochemical polymerization method, n-type conductive polymer polybenzodifuranone can be synthesized in air atmosphere in one step, without catalyst, high-temperature anaerobic environment and complex post-processing, the product conductivity is 1.157-18.28 S / cm.Process simplification, low cost, process controllable, can realize green scale preparation and industrialization application.

Description

Technical Field

[0001] This invention belongs to the field of organic conductive polymer material preparation technology, specifically relating to a polybenzodifuran dione and its potentiostatic polymerization preparation method. Background Technology

[0002] Conductive polymers possess unique optoelectronic properties and processability, making them promising candidates for applications in organic solar cells, transistors, capacitors, and sensors. Based on the type of charge carriers they carry, conductive polymers can be classified into p-type and n-type. P-type conductive polymers are widely used and mass-produced, such as poly(3,4-ethylenedioxythiophene):styrene sulfonate (PEDOT:PSS). However, the electrical properties and solution processability of n-type conductive polymers are mutually restrictive, resulting in limited research on them. Furthermore, these materials generally suffer from low conductivity, poor air stability, and low doping efficiency, severely hindering their practical application.

[0003] In the research on the preparation of p-type conductive polymers, electrochemical polymerization is widely used due to its advantages such as process controllability and high product purity. For example, Chinese patent application CN109346209A discloses a method for preparing needle-like nanostructured conductive polymer films i-PEDOT using a potentiostatic method. This method uses 3,4-ethylenedioxythiophene (EDOT) as a monomer, tetrabutylammonium perchlorate (TBAP) as a supporting electrolyte, and dichloromethane as a solvent. By applying a constant potential of 1.3-1.7V in a three-electrode system, a PEDOT film with a specific nanostructure was successfully deposited on the working electrode and applied to electrochromic materials. However, this method mainly focuses on the morphology control and performance optimization of p-type conductive polymers. Research on the synthesis of n-type conductive polymers is relatively lagging behind, mainly due to the common problems of low conductivity, poor air stability, and low doping efficiency of n-type polymers, which seriously restricts their practical application. Currently, the novel n-type conductive polymer polybenzo[1,2B:4,5B']difuran-2,6(3H,7H)dione (Nature 2022, 611, 271-277) has attracted widespread attention due to its excellent electrical conductivity and stability, providing new possibilities for the development of high-performance n-type conductive polymer materials. This reaction, using p-benzoquinone as a catalyst, achieves an extremely high electrical conductivity of 2000 S / cm through self-doping after chemical oxidative polymerization under high temperature and oxygen-free conditions. However, this method has stringent requirements for reaction conditions, relying on high temperature, an oxygen-free environment, and a suitable catalyst. Furthermore, post-reaction dialysis is necessary to obtain the polymer with high electrical conductivity.

[0004] To overcome the aforementioned limitations, electrochemical polymerization is considered a promising alternative due to its advantages such as process controllability, lack of the need for external catalysts, and high product purity. Therefore, developing a simple, mild reaction system that does not require high temperatures or oxygen isolation to directly prepare high-performance n-type conductive polymers has become a key technical challenge urgently needing to be addressed in this field. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide a polybenzodifuran dione and its constant potential polymerization preparation method, so as to solve the technical problems of the existing polybenzodifuran dione chemical synthesis method having harsh reaction conditions, requiring external catalysts and complicated post-processing.

[0006] To achieve the above objectives, the present invention employs the following technical solution: This invention discloses a method for preparing polybenzodifurandione by potentiostatic polymerization, comprising: Benzodifurandione and supporting electrolyte were dissolved in a polar aprotic solvent and mixed thoroughly to obtain an electrolyte. A platinum metal electrode was used as the working electrode and counter electrode, and a saturated calomel electrode was used as the reference electrode. The three electrodes were connected to a DC power supply and placed in the electrolyte. Electrochemical polymerization was carried out under an air atmosphere using a constant potential method. After the reaction was completed, the reaction solution was filtered and dried to obtain polybenzodifurandione.

[0007] Preferably, the polymerization temperature of the electrochemical polymerization reaction is 0-75℃.

[0008] Preferably, the polymerization time of the electrochemical polymerization reaction is 60-200 min.

[0009] Preferably, the oxidation potential of the electrochemical polymerization reaction is 0.7-3.5 V.

[0010] Preferably, the polar aprotic solvent is dimethyl sulfoxide, or a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide.

[0011] Preferably, the electrolyte is any one of NH4Cl, LiCl, and KClO4.

[0012] Preferably, the concentration of the electrolyte in the electrolyte solution is 0.1-0.4 mol / L.

[0013] Preferably, the concentration of benzodifurandione in the electrolyte is 5-20 mg / mL.

[0014] The present invention discloses a polybenzodifurandione, which is prepared by the above-mentioned constant potential polymerization method of polybenzodifurandione.

[0015] Preferably, the polybenzodifurandione is an n-type conductive polymer with a conductivity of 1.157-18.28 S / cm.

[0016] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a potentiostatic polymerization method for preparing polybenzodifurandione (BFDO). An electrochemical potentiostatic polymerization system for the n-type monomer BFDO is constructed. Using an electrolyte composed of a polar aprotic solvent, BFDO, and a supporting electrolyte, combined with a platinum electrode and a potentiostatic method, the polymerization of BFDO was successfully achieved in air. This method eliminates the need for harsh high-temperature, oxygen-free environments, external catalysts such as p-benzoquinone, and complex post-processing steps like dialysis; the product can be obtained simply through filtration and drying. The potentiostatic method provides a precise oxidation driving force, enabling the direct oxidative polymerization of the BFDO monomer on the electrode surface. The polar aprotic solvent effectively dissolves both the BFDO monomer and the supporting electrolyte, and also allows for enol tautomerization of the BFDO monomer, thus completing the polymerization under mild conditions. This method solves the technical problems of complex and demanding synthesis processes in existing n-type conductive polymers, simplifying the preparation method.

[0017] Furthermore, the polymerization temperature of the electrochemical polymerization reaction is 0-75℃. Based on the data from the examples in Table 1, a conductivity of 3.099 S / cm can be obtained at room temperature (approximately 25℃) (Example 1), while the conductivity increases to 18.28 S / cm and 15.46 S / cm, respectively, when polymerized at 50℃ (Example 4) and 75℃ (Example 5). This indicates that increasing the temperature within a certain range is beneficial for improving polymerization efficiency or enhancing the orderliness of the polymer chains, thereby improving electrical conductivity. Appropriate heating can increase the conductivity of the electrolyte, accelerate the monomer diffusion rate, and promote the polymerization reaction. This invention covers a wide range from low to high temperatures, ensuring both ease of operation at room temperature and allowing for performance optimization through heating, significantly enhancing process flexibility and industrial applicability.

[0018] Furthermore, the polymerization time of the electrochemical polymerization reaction is 60-200 min, ensuring the full progress of the polymerization reaction and the controllability of the process. As can be seen from the data of the examples, PBFDO with practical conductivity can be obtained within a polymerization time range of 60-90 min (e.g., in Example 4, the conductivity reached 18.28 S / cm after 60 min of polymerization). By optimizing the polymerization time of the electrochemical polymerization reaction, the polymerization efficiency and product quality are balanced, enabling the potentiostatic method to stably and controllably prepare high-performance PBFDO.

[0019] Furthermore, the oxidation potential of the electrochemical polymerization reaction is 0.7-3.5 V, which is the key electrochemical driving force for the effective polymerization of BFDO monomers. As shown in the examples, conductive polymers were successfully obtained at potentials of 2 V and 3 V, with conductivity ranging from 1.157 to 18.28 S / cm. The potential needs to be higher than the oxidation potential of the BFDO monomers to initiate polymerization, but too high a potential may lead to solvent or electrolyte decomposition, affecting product purity; too low a potential will prevent effective polymerization. The oxidation potential of 0.7-3.5 V ensures efficient initiation and stable progress of the polymerization reaction, while avoiding the occurrence of side reactions.

[0020] Furthermore, PBFDO can be successfully prepared using dimethyl sulfoxide (DMSO) or a mixture of DMSO and N,N-dimethylformamide as the polar aprotic solvent. Both pure DMSO and a mixture of DMSO and DMF can be successfully used. DMSO and DMF possess strong polarity, high dielectric constant, and good electrochemical stability, promoting the enol tautomerism of BFDO monomers. Simultaneously, their aprotic nature prevents proton transfer and other side reactions at the polymerization potential. They effectively stabilize the free radical cationic intermediates generated during polymerization and promote chain growth reactions, making them an indispensable medium for the successful potentiostatic polymerization of PBFDO.

[0021] Furthermore, the supporting electrolyte can be any one of NH4Cl, LiCl, and KClO4. Using NH4Cl (Examples 1-6), a conductivity of 2.027-18.28 S / cm can be obtained; using LiCl (Example 7), it is 1.408 S / cm; and using KClO4 (Example 8), it is 1.157 S / cm. This indicates that these inorganic salts can effectively act as supporting electrolytes and participate in the polymerization reaction, becoming doped into the polymer long chain. Moreover, the selected inorganic salts are lower in cost, more environmentally friendly, and easier to obtain, reducing production costs from the source and simplifying post-processing.

[0022] Furthermore, the supporting electrolyte concentration in the electrolyte solution is 0.1-0.4 mol / L. As seen in the examples, polymerization was successful when the NH4Cl concentration was 0.1 mol / L (Example 1) and 0.2 mol / L (Example 3), respectively. The electrolyte concentration needs to be high enough to ensure sufficient conductivity of the solution, reduce the ohmic voltage drop, and ensure accurate application of the electrode potential; however, excessively high concentrations may increase solution viscosity or trigger side reactions. The supporting electrolyte concentration of 0.1-0.4 mol / L provides a stable and efficient ionic environment for potentiostatic polymerization.

[0023] Furthermore, the concentration of benzodifuran dione in the electrolyte is 5-20 mg / mL. Monomer concentration is a key factor determining the polymerization kinetics and product molecular weight: when the concentration is too low, the flux of monomer diffusing to the electrode surface is insufficient, resulting in a slow polymerization rate, low yield, and a high likelihood of electrode side reactions; when the concentration is too high, the excessively high monomer concentration on the electrode surface may lead to an excessively rapid oxidation rate, instantly generating a large amount of oligomer precipitates, affecting the polymer's density and chain segment regularity, thus limiting further improvement in conductivity. By optimizing the monomer concentration range, the polymerization reaction was ensured to proceed stably at a controlled rate, guaranteeing sufficient yield and degree of polymerization while avoiding product structural defects caused by excessively rapid reactions, laying the foundation for obtaining conductivity properties of 1.157-18.28 S / cm.

[0024] This invention discloses a polybenzodifurandione (BFDO), which successfully achieves effective n-type doping and charge transport. During the electrochemical polymerization process, the oxidation driving force provided by the constant potential causes the BFDO monomer to polymerize and form a conjugated backbone, accompanied by the doping of supporting electrolyte cations, resulting in a stable n-type conductive state. Through an extremely simple electrochemical method, n-type PBFDO with practical conductivity can be obtained in an air atmosphere without a catalyst. This demonstrates the feasibility of preparing high-performance n-type polymers via an electrochemical route, opening up new research directions and industrialization pathways for further process optimization to improve conductivity, and solving the technical problem that existing n-type conductive polymers are difficult to obtain practically conductive products through simple methods. Attached Figure Description

[0025] Figure 1 The images shown are surface SEM images of polybenzodifurandione prepared in Examples 1-8 of this invention; wherein, (A) is Example 1; (B) is Example 2; (C) is Example 3; (D) is Example 4; (E) is Example 5; (F) is Example 6; (G) is Example 7; and (H) is Example 8. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Unless otherwise specified, all embodiments and preferred embodiments mentioned herein can be combined to form new technical solutions.

[0028] Unless otherwise specified, all the technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0029] In this invention, unless otherwise specified, percentage (%) or parts refer to weight percentage or parts relative to the composition.

[0030] Unless otherwise specified, the components or preferred components involved in this invention can be combined with each other to form new technical solutions.

[0031] In this invention, unless otherwise specified, the numerical range "ab" is an abbreviation for any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "6-22" indicates that the text already includes real numbers between "6-22", and "6-22" is simply an abbreviation for these numerical combinations.

[0032] The "scope" disclosed in this invention can be in the form of a lower limit and an upper limit, and can be one or more lower limits and one or more upper limits, respectively.

[0033] In this invention, the term "and / or" as used herein refers to any combination of one or more of the associated listed items, as well as all possible combinations, and includes such combinations.

[0034] Unless otherwise stated, the technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be used in this invention.

[0035] This invention provides a method for preparing polybenzodifurandione by potentiostatic polymerization, comprising: Using a DC power supply as the energy source, platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the DC power supply and placed in the electrolyte. The polymer was obtained by oxidative polymerization at an oxidation potential of 0.7-3.5 V and a polymerization temperature of 0-75 °C for 60-200 min using a constant potential method. After filtration and drying at 50-100 °C, polybenzodifurandione (PBFDO) was obtained. PBFDO is an n-type conductive polymer with a conductivity of 1.157-18.28 S / cm.

[0036] The electrolyte is a mixture of a polar aprotic solvent, benzodifurandione (BFDO), and a supporting electrolyte.

[0037] The polar aprotic solvent is dimethyl sulfoxide (DMSO), or a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide (DMF); the supporting electrolyte is any one of NH4Cl, LiCl, and KClO4; the concentration of the supporting electrolyte in the solution is 0.1-0.4 mol / L; the concentration of BFDO monomer in the electrolyte solution is 5-20 mg / mL.

[0038] This invention successfully prepared n-type conductive polymer PBFDO with a conductivity of 1.157-18.28 S / cm by combining specific electrolyte compositions (polar aprotic solvent, BFDO monomer concentration, and supporting electrolyte type) with optimized electrochemical polymerization process parameters (potential magnitude and polymerization time). The potentiostatic polymerization method employed is easy to control, with precisely adjustable parameters, avoiding potential side reactions and purification difficulties in chemical polymerization, ensuring product consistency and stability. The method is simple and reproducible. The polymer is directly generated on the electrode surface using the potentiostatic method, and the product can be obtained through simple filtration and drying without complex post-processing, resulting in a pure product.

[0039] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0040] Example 1 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.107g NH4Cl and 0.160g BFDO to 20 mL DMSO solution and stir well to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at a potential of 2V for 72 minutes at room temperature. Step 3: The solution after the reaction was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper and dried at 80°C to obtain polybenzodifuran diketone. The conductivity was tested by the four-probe method.

[0041] Example 2 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.107g NH4Cl and 0.160g BFDO to a mixed solution of 17 mL DMSO and 3 mL DMF and stir until homogeneous to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at a potential of 3.5V for 90 minutes at room temperature. Step 3: The solution after the reaction was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper. The film was dried at 60 °C to obtain polybenzodifuran diketone. The conductivity was tested by the four-probe method.

[0042] Example 3 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.428g NH4Cl and 0.100g BFDO to 20 mL DMSO solution and stir well to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at a potential of 2V for 60 minutes at room temperature. Step 3: The solution after the reaction was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper. The film was dried at 60 °C to obtain polybenzodifuran diketone. The conductivity was tested by the four-probe method.

[0043] Example 4 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.107g NH4Cl and 0.160g BFDO to 20 mL DMSO solution and stir well to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at 50°C and a potential of 2V for 60 minutes. Step 3: The solution after the reaction was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper. The film was dried at 60 °C to obtain polybenzodifuran diketone. The conductivity was tested by the four-probe method.

[0044] Example 5 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.214g NH4Cl and 0.160g BFDO to 20 mL DMSO solution and stir well to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at 75°C and a potential of 2V for 60 minutes. Step 3: The solution after the reaction was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper. The film was dried at 60 °C to obtain polybenzodifuran diketone. The conductivity was tested by the four-probe method.

[0045] Example 6 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.107g NH4Cl and 0.200g BFDO to 16 mL DMSO and 4 mL DMF solution and stir well to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at a potential of 2V for 200 minutes at room temperature. Step 3: The reaction solution was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper. The film was dried at 80 °C to obtain polybenzodifuran diketone. The conductivity was tested using the four-probe method.

[0046] Example 7 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.085g LiCl and 0.400g BFDO to 20 mL DMSO solution and stir well to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at 0°C and 2V for 200 min. Step 3: The reaction solution was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper. The film was dried at 80 °C to obtain polybenzodifuran diketone. The conductivity was tested using the four-probe method.

[0047] Example 8 A method for preparing polybenzodifurandione by potentiostatic polymerization includes: Step 1: Add 0.277g KClO4 and 0.160g BFDO to 20 mL DMSO solution and stir well to prepare the electrolyte; Step 2: Using platinum metal as the working electrode and counter electrode, and a saturated calomel electrode as the reference electrode, all three electrodes were connected to the electrochemical workstation and placed in the electrolyte. The scan was performed at a potential of 0.7V for 60 minutes at room temperature. Step 3: The reaction solution was filtered using organic filter paper with a pore size of 20 μm. After filtration, a PBFDO polymer film was formed on the surface of the filter paper. The film was dried at 80 °C to obtain polybenzodifuran diketone. The conductivity was tested using the four-probe method.

[0048] Table 1. Conductivity test results of polybenzodifurandiones prepared in Examples 1-8

[0049] Table 1 shows the conductivity test results of the polybenzodifurandiones obtained in Examples 1-8. As can be seen from the table, the conductivity of the polybenzodifurandiones obtained in this invention ranges from 1.157 to 18.28 S / cm. When NH4Cl is used as the supporting electrolyte, the resulting polymer exhibits even higher conductivity. In particular, the conductivity of the product obtained by polymerization under high-temperature conditions exceeds 10 S / cm. 1 On the order of magnitude of S / cm.

[0050] Figure 1 The images show surface SEM images of the polybenzodifuran diones prepared in Examples 1-8; where (A) is Example 1; (B) is Example 2; (C) is Example 3; (D) is Example 4; (E) is Example 5; (F) is Example 6; (G) is Example 7; and (H) is Example 8. Image analysis revealed an intrinsic correlation between the product's electrical conductivity and its surface microstructure: a clear morphology transition threshold (~10). 1 When the S / cm value is below a certain value, the product exhibits a fine needle-like structure; when it is above a certain value, it transforms into a coarse rod-like structure.

[0051] Taking Example 4 of the present invention as an example, it can be seen that the PBFDO polymerized by the electrochemical method of the present invention already has a certain conductivity; Figure 1 Images (D) and (E) show that the surface of polymer PBFDO is rod-shaped, while the surface of other polymer PBFDOs is needle-shaped, which is consistent with the results of higher conductivity in Examples 4 and 5. This invention is the first to successfully polymerize the n-type conductive polymer PBFDO in a simple and low-cost manner, paving a new path for its industrialization.

[0052] In summary, this invention provides a method for the electrostatic polymerization of polybenzodifuran dione (PBFDO). PBFDO is dissolved in a polar aprotic solvent, a supporting electrolyte is added, and platinum metal is used as both the working and counter electrodes, with a saturated calomel electrode serving as the reference electrode. Electrochemical polymerization is carried out in an air atmosphere at a constant potential, directly generating PBFDO on the electrode surface. This invention innovatively employs an electrostatic polymerization method to produce PBFDO, eliminating the need for additional catalysts and high-pressure or oxygen-isolated environments. Furthermore, this method exhibits excellent temperature adaptability, remaining highly efficient at room temperature and higher temperatures. The process is simple, easy to control, and significantly reduces costs, providing a new pathway for the green synthesis and large-scale preparation of n-type conductive polymers.

[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing polybenzodifurandione by potentiostatic polymerization, characterized in that, include: Benzodifurandione and supporting electrolyte are dissolved in a polar aprotic solvent and mixed evenly to obtain an electrolyte solution. Using a platinum metal electrode as the working electrode and the counter electrode, and a saturated calomel electrode as the reference electrode, the three electrodes were connected to a DC power supply and placed in the electrolyte. Electrochemical polymerization was carried out under an air atmosphere using a constant potential method. After the reaction was completed, the reaction solution was filtered and dried to obtain polybenzodifurandione.

2. The method for preparing polybenzodifurandione by constant potential polymerization according to claim 1, characterized in that, The polymerization temperature of the electrochemical polymerization reaction is 0-75℃.

3. The method for preparing polybenzodifurandione by potentiostatic polymerization according to claim 1, characterized in that, The polymerization time of the electrochemical polymerization reaction is 60-200 min.

4. The method for preparing polybenzodifurandione by potentiostatic polymerization according to claim 1, characterized in that, The oxidation potential of the electrochemical polymerization reaction is 0.7-3.5 V.

5. The method for preparing polybenzodifurandione by potentiostatic polymerization according to claim 1, characterized in that, The polar aprotic solvent is dimethyl sulfoxide, or a mixed solution of dimethyl sulfoxide and N,N-dimethylformamide.

6. The method for preparing polybenzodifurandione by potentiostatic polymerization according to claim 1, characterized in that, The supporting electrolyte is any one of NH4Cl, LiCl, and KClO4.

7. The method for preparing polybenzodifurandione by potentiostatic polymerization according to claim 1, characterized in that, The concentration of the supporting electrolyte in the electrolyte solution is 0.1-0.4 mol / L.

8. The method for preparing polybenzodifurandione by potentiostatic polymerization according to claim 1, characterized in that, The concentration of the benzodifurandione in the electrolyte is 5-20 mg / mL.

9. A polybenzodifuran diketone, characterized in that, It was prepared by the constant potential polymerization method of polybenzodifurandione according to any one of claims 1-8.

10. The polybenzodifuran diketone according to claim 9, characterized in that, The polybenzodifurandione is an n-type conductive polymer with a conductivity of 1.157-18.28 S / cm.

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