N-type conductive polymer and large-scale preparation method thereof

Abstract

The present invention discloses an n-type conductive polymer and a large-scale preparation method thereof, comprising the following steps: mixing a polymerized monomer with anhydride and DMSO, reacting under the protection of an inert gas, and obtaining an n-type conductive polymer. The present invention blends anhydride substances with dimethyl sulfoxide to generate an oxidizing complex in situ, thereby realizing low-cost large-scale preparation of n-type conductive polymers and other heteroatom-substituted analogs / blends. The present invention avoids the additional use of other oxidants and adopts relatively inexpensive anhydrides, which not only effectively reduces the material cost; at the same time, due to the volatility of anhydrides or their derivatives, they can be simply post-processed by vacuum concentration, further reducing the cost required for dialysis purification treatment in the prior art. In addition, the n-type conductive polymer of the present invention has a conductivity comparable to that of the prior art and has good storage stability, which is conducive to further promoting the industrialization of n-type conductive polymers.

Description

Technical Field

[0001] The invention belongs to the field of organic material processing and preparation, and in particular relates to an n-type conductive polymer and a large-scale preparation method thereof. Background Art

[0002] Conductive polymers refer to polymer materials with intrinsic conductivity, and their molecular structures usually contain conjugated long-chain structures with alternating single and double bonds. Delocalized π electrons can migrate on the molecular chain to form current, making the polymer material itself conductive. In addition, conductive polymers also have solution processability, mechanical toughness and good biocompatibility, which enable them to be very quickly applied to printed circuits, capacitors and bioelectronic devices through printing. Among them, the p-type conductive polymer poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS), which is dominated by the transport of positive charge carriers (holes), has been widely used in many fields due to its characteristics of aqueous solution processability, adjustable conductivity and high stability. However, the development of n-type conductive materials dominated by the transport of negative charge carriers (electrons) has always faced major challenges, with problems such as poor air stability and conductivity far lower than PEDOT.

[0003] Recently, the article Nature 2022,611,271 reported a new n-type conductive polymer, poly(benzodifurandione) (PBFDO). As a stable, high-conductivity solution-processable n-type conductive polymer, this polymer has brought new opportunities for the development of n-type conductive materials and has aroused widespread interest in various fields. The article J.Am.Chem.Soc.2023,145,3706 further improved the film-forming method to achieve a conductivity of more than 6000S / cm, representing one of the highest levels of current organic conductive materials. However, large-scale preparation process and cost are factors that must be considered for conductive polymer materials to further move towards practical industrial large-scale application. The n-type conductive polymer preparation methods disclosed in the currently reported articles and patent CN115960338B all require the addition of additional oxidants to achieve oxidative polymerization, such as tetramethylbenzoquinone, copper acetate, ferric chloride, etc., and the excess oxidant or oxidant reaction byproducts need to be removed by tedious dialysis, and the risk of metal ion residues may also be increased. These have led to an increase in the preparation process and cost of n-type conductive polymers, which is not conducive to the realization of its large-scale industrial preparation. Therefore, the development of a simpler, more environmentally friendly, and lower-cost n-type conductive polymer preparation method will greatly promote its large-scale application.

[0004] In summary, it is necessary to develop a new large-scale preparation method for n-type conducting polymers. Summary of the invention

[0005] The present invention provides a large-scale preparation method suitable for n-type conductive polymer poly(benzodifurandione) (PBFDO) and other heteroatom-substituted analogs / blends. The method does not directly add other organic / metallic oxidants, thereby effectively avoiding the introduction of metal ions and the cumbersome dialysis process required for removing oxidant residues during subsequent treatment. The present invention uses anhydride substances mixed with dimethyl sulfoxide (DMSO) to generate oxidizing active substances in situ in the reaction system, thereby achieving the polymerization of PBFDO and other heteroatom-substituted analogs / blends. At the same time, the by-products after the reaction are mainly corresponding acid products, which are easily removed by vacuum concentration, thereby reducing the post-processing process and cost required in the material preparation process. The present invention also further establishes a corresponding solvent recovery and reuse mechanism, thereby realizing low-cost large-scale preparation of n-type conductive polymers, making up for the deficiencies in the existing production and preparation process of n-type conductive polymers PBFDO and its derivatives, and further promoting the industrial large-scale preparation process of such substances.

[0006] An object of the present invention is to provide an n-type conductive polymer having the following structure:

[0007]

[0008] in,

[0009] The X is independently selected from O, S atom or NR;

[0010] The R is selected from a C1-C20 alkyl group or an alkyl derivative;

[0011] Said n and m are integers greater than or equal to 0;

[0012] Said m≤n.

[0013] Furthermore, the alkyl group is selected from a straight-chain alkylene group or a branched-chain alkylene group; one or more hydrogen atoms on the alkyl derivative are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkene, and alkyne groups.

[0014] Furthermore, the n is selected from a positive integer of 2-2000.

[0015] Another object of the present invention is to provide a large-scale preparation method of the above-mentioned n-type conductive polymer, wherein the large-scale preparation method of the n-type conductive polymer comprises the following steps:

[0016] The polymerizable monomer is mixed with anhydride and a solvent, and reacted under the protection of an inert gas to obtain an n-type conductive polymer;

[0017] The polymerizable monomer has the following structure:

[0018]

[0019] in,

[0020] The X is independently selected from O, S atom or NR;

[0021] The R is selected from a C1-C20 alkyl group or an alkyl derivative;

[0022] The solvent included DMSO.

[0023] Furthermore, the reaction formula for preparing the n-type conductive polymer and other heteroatom-substituted analogs / blends is as follows: Figure 1 shown.

[0024] Furthermore, the acid anhydride is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, caproic anhydride, 2-ethylhexanoic anhydride, nonanoic anhydride, lauric anhydride, palmitic anhydride, stearic anhydride, benzoic anhydride, phthalic anhydride, and isophthalic anhydride.

[0025] Furthermore, the solvent also includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylpyrrolidone.

[0026] Furthermore, the molar ratio of the acid anhydride to the polymerizable monomer is (0.5-4):1, and the molar ratio of the DMSO to the acid anhydride is ≥1.

[0027] Furthermore, the reaction temperature is 20-120°C and the reaction time is 10 min-6 h.

[0028] Furthermore, the inert gas is selected from one or more of argon and nitrogen.

[0029] Furthermore, a purification process is also included, and the purification process includes: adding a solvent and water to the system after the reaction, and then performing vacuum concentration.

[0030] Furthermore, it also includes a solvent recovery process, which includes: adding alkali to the solution collected by vacuum concentration, and then recovering the solvent under vacuum.

[0031] Furthermore, the purification process includes: adding additional reaction solvent to the reaction system to dilute the viscosity of the reaction solution, adding a trace amount of water to quench and terminate the reaction, and using vacuum concentration to remove volatile anhydride substances or acid substances generated in the reaction.

[0032] Optionally, the purification process also includes: a simple dialysis process to remove small molecular weight substances in the polymer and optimize the molecular weight of the polymer material to meet the subsequent application requirements in different scenarios.

[0033] Furthermore, the solvent recovery process comprises: mixing the solutions collected by vacuum concentration in the previous steps, adding alkaline substances to the solutions to neutralize the acidic substances remaining, and adding the resulting solution to a solvent recovery device to recover under vacuum;

[0034] The alkaline substance is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, etc.;

[0035] The temperature of the solvent recovery device is 40-120° C., and the vacuum degree of the vacuum is 1-300 mbar.

[0036] The present invention adopts a strategy of in-situ generation of oxidative active substances. By mixing anhydride substances with DMSO, an oxidative complex can be generated in-situ during the reaction process, thereby realizing large-scale preparation of n-type conductive polymers and other heteroatom-substituted analogs / blends. Figure 2 Taking acetic anhydride as an example, a schematic diagram of the formation of an oxidizing substance after the anhydride substance is mixed with DMSO is shown. At the same time, the present invention further provides a full process suitable for the large-scale preparation of n-type conductive polymers, which greatly reduces solvent consumption and waste liquid treatment through solvent recovery and reuse, and is conducive to promoting the industrialization of n-type conductive polymers. The large-scale preparation method of n-type conductive polymers described in the present invention is shown in Figure 3 middle.

[0037] Compared with the prior art, the main advantages of the present invention are as follows:

[0038] 1. The large-scale preparation method and process of n-type conductive polymers provided by the present invention avoids the additional use of other oxidants, and adopts a strategy of in-situ generation of oxidative active species using relatively inexpensive acid anhydride substances, which not only effectively reduces the material cost during synthesis; at the same time, due to the volatility of acid anhydrides or their derivatives, they can be simply post-processed by vacuum concentration, further reducing the cost required for dialysis purification treatment in previously reported methods;

[0039] 2. The present invention further realizes the recycling of solvents by alkaline neutralization and vacuum recovery of the waste solution in the process, effectively reducing the generation of waste solution in the whole process, further reducing the cost of waste liquid treatment and realizing environmentally friendly sustainable production;

[0040] 3. Under the premise of greatly reducing material costs and time costs, the n-type conductive polymer prepared by the present invention can obtain a conductivity comparable to that reported previously, which will be beneficial to further promote the industrialization of n-type conductive polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1This is the reaction formula for preparing n-type conductive polymers and other heteroatom-substituted analogs / blends of the present invention.

[0042] Figure 2 This is a schematic diagram of the formation of oxidizing substances after an acid anhydride substance, such as acetic anhydride, is mixed with DMSO.

[0043] Figure 3 The flowchart is a large-scale preparation method of an n-type conductive polymer according to the present invention.

[0044] Figure 4 This is a flow chart of the preparation and recovery of PBFDO in Example 6.

[0045] Figure 5 This is a flow chart of the preparation and recovery of PBFDO in Example 7.

[0046] Figure 6 The purity test result of the recovered solvent DMAc by gas chromatography in Example 7 is shown in FIG.

[0047] Figure 7 This is a conductivity test curve of the n-type conductive polymer obtained in Example 1.

[0048] Figure 8 This is a conductivity test curve of the n-type conductive polymer obtained in Example 7.

[0049] Fig. 9 This is a conductivity test curve of the n-type conductive polymer obtained in Comparative Example 1. DETAILED DESCRIPTION

[0050] In order to more clearly illustrate the technical solution of the present invention, the following examples are listed. Unless otherwise stated, the raw materials, reactions and post-treatment methods shown in the examples are common raw materials on the market and technical methods well known to those skilled in the art.

[0051] Example 1

[0052] A large-scale preparation method of PBFDO comprises the following steps:

[0053]

[0054] Under nitrogen protection, benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas:30272-74-3) (50g, 0.263mol) was dissolved in 3500mL of ultra-dry DMSO to obtain a mixture; then 40mL of acetic anhydride was added. The mixed solution was stirred at 80°C for 30min to obtain a viscous solution. After cooling to room temperature, 500mL of DMSO was added for dilution, and 10mL of deionized water was added to terminate the reaction, and then stirring was continued at room temperature for 20min. The obtained solution was concentrated using a vacuum rotary evaporator to obtain a DMSO solution of the target product.

[0055] Example 2

[0056] A large-scale preparation method of PBFDO comprises the following steps:

[0057]

[0058] Under nitrogen protection, benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas:30272-74-3) (50g, 0.263mol) was dissolved in 3500mL of ultra-dry DMSO to obtain a mixture; then 65mL of propionic anhydride was added. The mixed solution was stirred at 65°C for 40min to obtain a viscous solution. After cooling to room temperature, 500mL of DMSO was added for dilution, and 15mL of deionized water was added to terminate the reaction, and then stirring was continued at room temperature for 20min. The obtained solution was concentrated using a vacuum rotary evaporator to obtain a DMSO solution of the target product.

[0059] Example 3

[0060] A large-scale preparation method of PBFDO comprises the following steps:

[0061]

[0062] Under argon protection, benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas:30272-74-3) (50g, 0.263mol) was dissolved in 3500mL of ultra-dry DMAc to obtain a mixture; then 60mL of acetic anhydride and 100mL of DMSO were mixed and added to the reaction system. The mixed solution was stirred at 100°C for 60min to obtain a viscous solution. After cooling to room temperature, 500mL of DMAc was added for dilution, and 20mL of deionized water was added to terminate the reaction, and then stirring was continued at room temperature for 20min. The obtained solution was concentrated using a vacuum rotary evaporator to obtain a DMAc solution of the target product.

[0063] Example 4

[0064] A large-scale preparation method of poly(benzodithiophenedione) comprises the following steps:

[0065]

[0066] Under nitrogen protection, benzo[1,2-b:4,5-b']dithiophene-2,6(3H,7H)-dione (100 mg, 0.45 mmol) was dissolved in 10 mL of ultra-dry DMSO to obtain a mixture; then 90 μL of acetic anhydride was added. The mixed solution was stirred at 40 °C for 50 min to obtain a viscous solution. After cooling to room temperature, 2 mL of DMSO was added for dilution, and 50 μL of deionized water was added to terminate the reaction, and then stirring was continued at room temperature for 20 min. The obtained solution was concentrated using a vacuum rotary evaporator to obtain a DMSO solution of the target product.

[0067] Example 5

[0068] A large-scale preparation method of poly(benzodipyrrole diketo) comprises the following steps:

[0069]

[0070] Under nitrogen protection, 1,5-dipropyl-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione (150 mg, 0.55 mmol) was dissolved in 10 mL of ultra-dry DMSO to obtain a mixture; then 100 μL of acetic anhydride was added. The mixed solution was stirred at 100 °C for 6 h and then cooled to room temperature. 50 μL of deionized water was added to the reaction system to terminate the reaction, and then stirring was continued at room temperature for 20 min. The resulting solution was then concentrated using a vacuum rotary evaporator to obtain a DMSO solution of the target product.

[0071] Example 6

[0072] Based on Example 1, PBFDO was prepared using acetic anhydride and DMSO as the solvent system, and was dialyzed and purified, and the resulting dialysis waste was recovered and reused:

[0073] Under nitrogen protection, benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas:30272-74-3) (50g, 0.263mol) was dissolved in 3500mL of recovered DMSO to obtain a mixture; then 60mL of acetic anhydride was added. The mixed solution was stirred at 80°C for 30min to obtain a viscous solution. After cooling to room temperature, 500mL of recovered DMSO was added for dilution, and 10mL of deionized water was added to terminate the reaction, and then stirring was continued at room temperature for 20min. The obtained solution was loaded into a dialysis bag with a molecular weight cutoff of 10kDa, immersed in recovered DMSO (20L), and dialyzed for 36h. The product in the dialysis bag was collected and concentrated using a vacuum rotary evaporator to obtain a DMSO solution of the target product. At the same time, the solution in the rotary evaporator and the DMSO solution outside the dialysis bag were collected, mixed, and about 50 g of sodium hydroxide was added and stirred at room temperature for 20 min. After filtering, the obtained filtrate was added to a vacuum solvent recovery device, and the solution components were collected at 90° C. and 10 mbar to obtain recovered DMSO (collection was stopped when about 5-10% of the volume remained) for recycling.

[0074] Figure 4 This is a flow chart of the preparation and recovery of PBFDO in Example 6.

[0075] Example 7

[0076] Based on Example 1, DMSO was used as the solvent system, acetic anhydride was used to prepare PBFDO, and DMAc was used for dialysis purification to complete the solvent exchange, and the generated dialysis waste liquid was recovered and reused:

[0077] Under nitrogen protection, benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas:30272-74-3) (50g, 0.263mol) was dissolved in 3500mL of recovered DMSO to obtain a mixture; then 60mL of acetic anhydride was added. After the mixed solution was stirred at 80°C for 30min, a viscous solution was obtained. After cooling to room temperature, 500mL of recovered DMAc was added for dilution, and 10mL of deionized water was added to terminate the reaction, and then stirring was continued at room temperature for 20min. After that, the obtained solution was first concentrated using a vacuum rotary evaporator to remove some of the anhydride / acidic substance residues and water. Then, the obtained solution was loaded into a dialysis bag with a molecular weight cutoff of 10kDa and immersed in the recovered DMAc, using about 20L each time, and replaced once after dialysis for 36h. The product in the dialysis bag was collected and concentrated using a vacuum rotary evaporator to obtain a DMAc solution of the target product. The solution outside the dialysis bag was collected, combined with the part collected by vacuum concentration, and about 30 g of sodium hydroxide and 30 g of anhydrous magnesium sulfate were added and stirred at room temperature for 20 min. After filtration, the obtained filtrate was added to a vacuum solvent recovery device, and the solution components were collected at 65° C. and 50 mbar to obtain the recovered DMAc (the collection was stopped when about 25% of the volume remained) for recycling. The recovered DMAc solution was determined by gas chromatography to have a purity of more than 99.5%.

[0078] Figure 5 This is a flow chart of the preparation and recovery of PBFDO in Example 7.

[0079] Figure 6 The purity test result of the recovered solvent DMAc by gas chromatography in Example 7 is shown in FIG.

[0080] Table 1 shows the purity test results of the recovered solvent DMAc by gas chromatography in Example 7.

[0081] Table 1 Gas chromatography purity test results

[0082] Serial number Compound content(%) Remark 1 N,N-Dimethylacetamide 99.94 / 2 N-Methylacetamide 0.02 / 3 N,N-Dimethylpropionamide 0.04 /

[0083] Comparative Example 1

[0084] This comparative example adopts the PBFDO preparation method disclosed in Nature 2022,611,271 for large-scale preparation, comprising the following steps:

[0085]

[0086] Under argon protection, benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas:30272-74-3) (50g, 0.263mol) and 2,3,5,6-tetramethyl-1,4-benzoquinone (64.8g, 0.395mol) were dissolved in 3350mL of ultra-dry DMSO to obtain a mixture; the mixture was then stirred at 100°C for about 3.5h to obtain a viscous solution. After the reaction solution was cooled to room temperature, 500mL of DMSO was added for dilution, and the mixed solution was stirred at room temperature for 20min. The obtained solution was placed in a dialysis bag with a molecular weight cutoff of 10kDa and immersed in DMSO for dialysis. The product in the dialysis bag was collected and concentrated using a vacuum rotary evaporator to obtain a DMSO solution of the target product.

[0087] In this comparative example, in order to ensure the complete removal of the oxidant residue and its reaction products, it is usually necessary to perform 4 or more solvent changes, using about 20L each time and dialysis for 36h. A total of about 8 days of dialysis are required, and the solvent consumption is close to 100L. The material, recycling, waste liquid treatment and process time costs are greatly increased. At the same time, the price of the quinone oxidant used is also relatively high, much higher than the solution in Example 1 or Example 6.

[0088] Comparative Example 2

[0089] This comparative example adopts the PBFDO preparation method disclosed in the document J.Am.Chem.Soc.2023,145,3706 for large-scale preparation, comprising the following steps:

[0090]

[0091] Benzo[1,2-b:4,5-b']difuran-2,6(3H,7H)-dione (cas:30272-74-3) (50g, 0.263mol) and copper acetate (10.0g, 0.05mol) were dissolved in 3350mL of ultra-dry DMSO to obtain a mixture; the mixture was then stirred at 100°C for about 30min to obtain a viscous solution. After the reaction solution was cooled to room temperature, 500mL of DMSO was added for dilution, and the mixed solution was stirred at room temperature for 20min. The obtained solution was placed in a dialysis bag with a molecular weight cutoff of 10kDa and immersed in DMSO for dialysis. The product in the dialysis bag was collected, filtered through a filter membrane with a pore size of 0.45μm, and concentrated using a vacuum rotary evaporator to obtain a DMSO solution of the target product.

[0092] In this comparative example, in order to ensure the complete removal of the oxidant residue and its reaction products, it is usually necessary to perform 2 or more solvent changes, using about 20L each time and dialysis for 36h. A total of about 5 days of dialysis are required, and the solvent consumption is close to 50L. At the same time, a small amount of polymer precipitation is found during the implementation process, requiring additional filtration operations, which may be caused by the interaction between metal ions and polymers and affect the reproducibility of the implementation method.

[0093] Test Example 1

[0094] The polymer solutions obtained in Examples 1-3, Example 7, and Comparative Example 1 were respectively formed into films on glass substrates and dried in vacuo. The conductivity (σ) test was performed using the four-probe method, and the calculation formula was σ=IL / VWd, where I is the current, V is the voltage, L is the voltage probe spacing (here 3.6 mm), W is the film width (here 10 mm), and d is the film thickness (here about 3 μm). The obtained conductivity, process time, and amount of solvent consumed are summarized in Table 2, where the voltage-current curves of Example 1, Example 7, and Comparative Example 1 are shown in Table 2. Figure 7-9 shown.

[0095] Figure 7 This is a conductivity test curve of the n-type conductive polymer obtained in Example 1.

[0096] Figure 8 This is a conductivity test curve of the n-type conductive polymer obtained in Example 7.

[0097] Fig. 9 This is a conductivity test curve of the n-type conductive polymer obtained in Comparative Example 1.

[0098] Table 2 Conductivity test results, process time and solvent consumption of n-type conductive polymers under different embodiments

[0099]

[0100]

[0101] According to Table 2 and Figure 7-9 It can be seen that the n-type conductive polymer prepared by the method provided by the present invention has a conductivity comparable to that of the previously disclosed method, and the process flow (time cost) and solvent consumption (material cost) are greatly reduced, which will be beneficial to improving production efficiency.

[0102] Test Example 2

[0103] The stability of the polymer solution obtained in Example 7 was monitored under different conditions. The stability monitoring results are shown in Tables 3-5.

[0104] Table 3 Monitoring of storage stability of n-type conductive polymer solution prepared in Example 7 at low temperature

[0105]

[0106] Table 4 Storage stability monitoring of n-type conductive polymer solution prepared in Example 7 at room temperature

[0107]

[0108] Table 5 Storage stability monitoring of n-type conductive polymer solution prepared in Example 7 at 60°C

[0109]

[0110] According to Tables 3-5, it can be concluded that the n-type conductive polymer solution prepared by the present invention exhibits good stability when stored at low temperature (-2-6°C), and the conductivity decays within 15% after being placed at room temperature for 180 days, and still has a conductivity of more than 1600S / cm after being stored at 60°C for 90 days. The above results prove that the method proposed by the present invention can prepare n-type conductive polymer solutions with high stability on a large scale at low cost, thereby solving the bottleneck problems of low conductivity, poor stability and high cost currently faced by the field of n-type conductive polymers.

[0111] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0112] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A large-scale preparation method of an n-type conductive polymer, characterized in that: The n-type conductive polymer has the following structure: in, The X is independently selected from O, S atom or NR; The R is selected from a C1-C20 alkyl group or an alkyl derivative; Said n and m are integers greater than or equal to 0; m≤n; The large-scale preparation method of the n-type conductive polymer comprises the following steps: The polymerizable monomer is mixed with anhydride and a solvent, and reacted under the protection of an inert gas to obtain an n-type conductive polymer; The polymerizable monomer has the following structure: in, The X is independently selected from O, S atom or NR; The R is selected from a C1-C20 alkyl group or an alkyl derivative; The solvent included DMSO.

2. The large-scale preparation method of n-type conductive polymer according to claim 1, characterized in that: The acid anhydride is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, caproic anhydride, 2-ethylhexanoic anhydride, nonanoic anhydride, lauric anhydride, palmitic anhydride, stearic anhydride, benzoic anhydride, phthalic anhydride, and isophthalic anhydride.

3. The large-scale preparation method of n-type conductive polymer according to claim 1, characterized in that: The solvent further comprises one or more of N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylpyrrolidone.

4. The large-scale preparation method of n-type conductive polymer according to claim 1, characterized in that: The molar ratio of the acid anhydride to the polymerizable monomer is (0.5-4):1, and the molar ratio of the DMSO to the acid anhydride is ≥1.

5. The large-scale preparation method of n-type conductive polymer according to claim 1, characterized in that: The reaction temperature is 20-120°C and the reaction time is 10 min-6 h.

6. The large-scale preparation method of n-type conductive polymer according to claim 1, characterized in that: The method also includes a purification process, which includes: adding a solvent and water to the system after the reaction, and then performing vacuum concentration.

7. The large-scale preparation method of n-type conductive polymer according to claim 6, characterized in that: The method also includes a solvent recovery process, which includes: adding a base to the solution collected by vacuum concentration, and then recovering the solvent under vacuum.

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