Polymer, PEDOT dispersion and preparation method and application thereof

Abstract

The invention relates to the technical field of conductive macromolecules, in particular to a polymer, a PEDOT dispersoid and a preparation method and application of the PEDOT dispersoid. The polymer has a structure as shown in a formula (I), or has a stereoisomer, a nitrogen oxide, a hydrate, a solvate or a salt thereof with the structure as shown in the formula (I), wherein R1 is selected from H and C1-C6 alkyl; r2 is selected from F, Cl, Br and I; x, y and z are respectively and independently selected from any integer in the range of 2-300; '+' represents positive charge; '-' represents negative charge; "Represents connection to a repeating unit or H; ''refers to electrostatic acting force. The polymer is used as a main component in the PEDOT dispersion, can improve the conductivity and heat resistance of the PEDOT dispersion after film formation, and is beneficial to reducing the resistance of a capacitor, improving the capacity extraction rate of the capacitor and finally prolonging the service life of the capacitor when being applied to the capacitor. Formula (1)

Description

Technical Field

[0001] This invention relates to the field of conductive polymer technology, and in particular to a polymer, a PEDOT dispersion, its preparation method and application. Background Technology

[0002] As the material connected to the negative electrode in electronic components, cathode materials require good conductivity and stability. The conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is widely used in solar cells, electronic components, and antistatic coatings due to its simple molecular structure, small band gap, high conductivity, good environmental stability, and high-temperature resistance. However, PEDOT's insoluble and infusible properties make its processing difficult, limiting its application range. To improve PEDOT's solubility, sodium poly(4-vinylbenzenesulfonate) (PSSNa, or PSS for short) is typically used as a dopant.

[0003] However, the conductivity of existing commercially available PEDOT / PSS dispersions is poor and needs improvement. In aqueous solution, PEDOT / PSS forms a dispersion with PEDOT as the core and PSS as the shell. Since PSS is non-conductive, it hinders electron transfer within the PEDOT chains. Therefore, there is an urgent need to provide a method to improve the dispersion structure and enhance the electron transfer efficiency between PEDOT chains. Summary of the Invention

[0004] This invention aims to at least partially solve one of the technical problems in related technologies. To this end, this invention provides a polymer, a PEDOT dispersion, a method for preparing the same, and its applications. The polymer (PMCPMA-g-PSS / PEDOT), as the main component in the PEDOT dispersion, can improve the conductivity and heat resistance of the PEDOT dispersion after film formation. Its application in capacitors helps reduce capacitor resistance, increase capacitance extraction efficiency, and ultimately improve the capacitor's lifespan.

[0005] Therefore, in a first aspect, the present invention provides a polymer having the structure shown in formula (I), or a stereoisomer, nitride, hydrate, solvate, or salt thereof having the structure shown in formula (I): Equation (I) in: R1 is selected from H and C1-C6 alkyl groups; R2 is selected from F, Cl, Br, and I; x, y, and z are each independently selected from any integer in the range of 2 to 300; "+" indicates a positive charge; "-" indicates a negative charge; " " represents connection to a repeating unit or H; "┈" refers to electrostatic force.

[0006] The polymer (PMCPMA-g-PSS / PEDOT) provided by this invention is the main component in the PEDOT dispersion, which can improve the electrical conductivity and heat resistance of the PEDOT dispersion after film formation.

[0007] According to an embodiment of the present invention, R1 is selected from H, methyl, ethyl, and tert-butyl; R2 is selected from Cl and Br; x is selected from 2-200; preferably 2-150; preferably 5-100; preferably 10-80; more preferably 10-50; y is selected from 2-200; preferably 2-150; preferably 2-100; preferably 2-50; more preferably 2-30; z is selected from 2-200.

[0008] Therefore, the dispersion prepared by the polymer can improve the conductivity and heat resistance of the PEDOT dispersion after film formation. When applied to capacitors, it can help reduce capacitor resistance, increase capacitor capacitance extraction rate, and ultimately improve capacitor lifespan.

[0009] According to an embodiment of the present invention, the polymer has the following structural formula: (I-1) (I-2) (I-3) or (I-4).

[0010] A second aspect of the present invention provides a PEDOT dispersion comprising the polymer described in the first aspect and the EDOT monomer.

[0011] The PEDOT dispersion provided by this invention exhibits good electrical conductivity and heat resistance after film formation. When applied to capacitors, it helps to reduce capacitor resistance, increase capacitor capacitance extraction rate, and improve capacitor performance.

[0012] According to an embodiment of the present invention, the mass ratio of the polymer to the EDOT monomer in the PEDOT dispersion is (20-50):(1-20), preferably (30-50):(1-10).

[0013] According to an embodiment of the present invention, the PEDOT dispersion further includes water and dimethyl sulfoxide, wherein the mass ratio of the polymer, EDOT monomer, dimethyl sulfoxide and water in the PEDOT dispersion is (20-50):(1-20):(50-200):(200-500), preferably (30-50):(1-10):(100-200):(200-400).

[0014] According to an embodiment of the present invention, the solid content of the PEDOT dispersion is 1%-15%, preferably 1%-10%, and more preferably 4%-8%.

[0015] A third aspect of the present invention provides a method for preparing a PEDOT dispersion, comprising the following steps: The polymer PMCPMA-g-PSS is reacted with EDOT monomer to obtain a mixture containing the polymer described in the first aspect or the PEDOT dispersion described in the second aspect. The polymer PMCPMA-g-PSS has the structure shown in formula (II): Equation (II), R1, R2, x, y are as described in the first aspect.

[0016] The PEDOT dispersion can be prepared using the method provided by the present invention. The PEDOT dispersion has good electrical conductivity and heat resistance.

[0017] According to an embodiment of the present invention, the method further includes: The polymer PMCPMA-g-PSS, EDOT monomer, oxidant, first catalyst and pH adjuster are mixed to carry out the first reaction to obtain a mixture.

[0018] According to an embodiment of the present invention, the mass ratio of the EDOT monomer to the polymer PMCPMA-g-PSS is (1-10):(1-20), preferably (1-10):(1-15), more preferably (1-10):(1-10), more preferably (1-5):(1-10), and even more preferably (1-5):(1-5).

[0019] According to embodiments of the present invention, the oxidant includes one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0020] According to an embodiment of the present invention, the molar ratio of the oxidant to the EDOT monomer is (0.3-3):1, preferably (0.3-2):1, and more preferably (0.3-1):1. If too much oxidant is used, it may trigger side reactions, reduce the purity of the product, and increase the impurity content; if too little oxidant is used, it will not be fully oxidized.

[0021] According to an embodiment of the present invention, the first catalyst comprises ferric sulfate.

[0022] According to an embodiment of the present invention, the molar ratio of the first catalyst to the EDOT monomer is (0.001-0.006):1, preferably (0.001-0.005):1, more preferably (0.001-0.004):1, and even more preferably (0.001-0.003):1. Therefore, the first catalyst can catalyze the reaction to proceed fully without increasing cost or impurity content.

[0023] According to an embodiment of the present invention, the temperature of the first reaction is 10 °C-40 °C, preferably 20 °C-30 °C. Therefore, the reaction can proceed sufficiently.

[0024] According to an embodiment of the present invention, the first reaction takes 15 h to 30 h. Therefore, the reaction can proceed sufficiently.

[0025] According to an embodiment of the present invention, the pH adjuster includes acetic acid.

[0026] According to an embodiment of the present invention, the first reaction is carried out in a mixed solvent of dimethyl sulfoxide and water.

[0027] According to a specific embodiment of the present invention, the molar ratio of the dimethyl sulfoxide to the water is 1:(2-20).

[0028] According to an embodiment of the present invention, the solvent of the mixture includes dimethyl sulfoxide and water.

[0029] According to an embodiment of the present invention, the method further includes the following steps for preparing the polymer PMCPMA-g-PSS: The polymer PMCPMA, sodium 4-vinylbenzenesulfonate, a second catalyst, and a ligand are mixed to carry out a second reaction to obtain the polymer PMCPMA-g-PSS. The polymer PMCPMA has the structure shown in formula (Ⅲ): Equation (Ⅲ); R1, R2, x are as described in the first aspect.

[0030] According to an embodiment of the present invention, the molar ratio of sodium 4-vinylbenzenesulfonate to the polymer PMCPMA is 1000:(1-300).

[0031] According to an embodiment of the present invention, the molar ratio of the second catalyst to the polymer PMCPMA is (1-300):(1-10). Therefore, the second catalyst can catalyze the reaction to proceed fully without increasing cost or impurity content.

[0032] According to an embodiment of the present invention, the second catalyst comprises at least one of cuprous bromide, cuprous chloride, and cuprous sulfate. Therefore, the copper catalyst exhibits good catalytic effect for the second reaction.

[0033] According to an embodiment of the present invention, the ligand is N,N,N ' ,N ' ,N One or more of ''-pentamethyldiethylenetriamine (PMDETA), 2,2'-bipyridine (bpy), and tris(2-methylaminoethyl)amine (MeTREN).

[0034] According to an embodiment of the present invention, the molar ratio of the ligand to the polymer PMCPMA is (1-300):(1-10).

[0035] According to an embodiment of the present invention, the second reaction is carried out in the presence of tetrahydrofuran.

[0036] According to an embodiment of the present invention, the temperature of the second reaction is 30 °C-80 °C. Therefore, the reaction can proceed sufficiently.

[0037] According to an embodiment of the present invention, the second reaction takes 2 h to 30 h. Therefore, the reaction can proceed sufficiently.

[0038] According to an embodiment of the present invention, the method further includes the following steps for preparing the polymer PMCPMA: The intermediate is obtained by reacting acrylate with formaldehyde. The intermediate was reacted with 2-halopropionic acid to obtain the monomer MCPMA; The monomer MCPMA, chain transfer agent, and initiator are subjected to RAFT polymerization to obtain the polymer PMCPMA; The monomer MCPMA has the structure shown in formula (Ⅳ): Equation (Ⅳ), where R1 and R2 are as described in the first aspect.

[0039] According to embodiments of the present invention, the acrylate includes one of methyl acrylate, ethyl acrylate, and tert-butyl acrylate.

[0040] According to an embodiment of the present invention, the molar ratio of acrylate to formaldehyde is (1-5):(1-5).

[0041] According to an embodiment of the present invention, the reaction of the acrylate with formaldehyde is carried out in a mixed solvent of THF and deionized water, wherein the THF and deionized water have the same volume.

[0042] According to an embodiment of the present invention, the reaction of the acrylate with formaldehyde further requires the addition of 1,4-diazabicyclo[2.2.2]octane (DABCO) and a base, wherein 1,4-diazabicyclo[2.2.2]octane (DABCO) plays a catalytic role in the reaction, and the base includes triethylamine.

[0043] According to an embodiment of the present invention, the reaction temperature of the acrylate with formaldehyde is 20 ℃-30 ℃, and the reaction time is 1 h-5 h.

[0044] According to an embodiment of the present invention, the acrylate reacts with formaldehyde at 20 ℃-30 ℃ for 1 h-5 h, and then the temperature is raised to 50 ℃-70 ℃ for another 20 h-30 h.

[0045] According to an embodiment of the present invention, the 2-halopropionic acid includes one of 2-chloropropionic acid and 2-bromopropionic acid.

[0046] According to an embodiment of the present invention, the molar ratio of the intermediate to 2-halopropionic acid is (1-5):(1-5).

[0047] According to an embodiment of the present invention, the intermediate reacts with 2-halopropionic acid in the solvent dichloromethane.

[0048] According to an embodiment of the present invention, the reaction of the intermediate with 2-halopropionic acid further requires the addition of p-dimethylaminopyridine (DMAP) and... N- Cyclohexylsuccinimide (DCC), in which p-dimethylaminopyridine (DMAP) is used as a catalyst. N- Cyclohexylsuccinimide (DCC) is a dehydrating condensing agent.

[0049] According to an embodiment of the present invention, the molar ratio of p-dimethylaminopyridine (DMAP) to the intermediate is (0.01-0.1):1. N- The molar ratio of cyclohexylsuccinimide (DCC) to the intermediate is (0.5-1.5):1.

[0050] According to an embodiment of the present invention, the intermediate reacts with 2-halopropionic acid at a temperature of -5 °C to 0 °C for a time of 1 h to 24 h.

[0051] According to an embodiment of the present invention, the chain transfer agent is isopropyl phenyl dithiobenzoate (CDB).

[0052] According to an embodiment of the present invention, the molar ratio of the chain transfer agent to the monomer MCPMA is (0.01-0.1):1.

[0053] According to embodiments of the present invention, the initiator includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate.

[0054] According to an embodiment of the present invention, the molar ratio of the initiator to the monomer MCPMA is (0.01-0.05):1.

[0055] According to an embodiment of the present invention, the temperature of the RAFT polymerization reaction is 50 °C-90 °C. Therefore, the reaction can proceed fully.

[0056] According to an embodiment of the present invention, the RAFT polymerization reaction takes 10 h to 30 h. Therefore, the reaction can proceed sufficiently.

[0057] A fourth aspect of the present invention provides a polymer PMCPMA-g-PSS having the structure shown in formula (II), or a stereoisomer, nitride, hydrate, solvate, or salt thereof having the structure shown in formula (II): Equation (II), where R1, R2, x, and y are as described in the first aspect.

[0058] The polymer PMCPMA-g-PSS provided by this invention is an amphiphilic graft copolymer that can be used to prepare the aforementioned PEDOT dispersion.

[0059] The fifth aspect of the present invention provides the use of the polymer described in the first aspect, or the PEDOT dispersion described in the second aspect, or the PEDOT dispersion obtained according to the method described in the third aspect, or the polymer PMCPMA-g-PSS described in the fourth aspect, in solid capacitors.

[0060] The advantages of this invention over the prior art are: This invention provides a novel PEDOT dispersion based on the amphiphilic graft copolymer PMCPMA-g-PSS. This dispersion improves the conductivity of the PEDOT dispersion film, reduces the resistance of the resulting capacitor, increases the capacitance extraction rate, and extends the service life.

[0061] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Detailed Implementation

[0062] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0063] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Furthermore, in the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0064] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0065] To facilitate understanding of the invention, certain technical and scientific terms are specifically defined below. Unless otherwise expressly defined elsewhere in this document, all other technical and scientific terms used herein have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains.

[0066] In this document, the terms “comprising” or “including” are open-ended expressions, meaning they include the contents specified in this invention but do not exclude other aspects.

[0067] In this document, the terms “optionally,” “optionally,” or “optionally” generally refer to an event or condition that may, but may not, occur, and the description includes both cases in which the event or condition occurs and cases in which the event or condition does not occur.

[0068] Terminology Definitions and Explanations Unless otherwise stated, the definitions of groups and terms recorded in this application specification and claims, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, and definitions of specific compounds in the examples, can be arbitrarily combined and combined with each other. Such combinations and combinations of group definitions and compound structures shall fall within the scope of this application specification.

[0069] PEDOT: Poly(3,4-ethylenedioxythiophene); EDOT: 3,4-ethylenedioxythiophene; PSS: Sodium poly(4-vinylbenzenesulfonate); SSNa: Sodium 4-vinylbenzenesulfonate; CDB: Isopropylphenyl dithiobenzoate; AIBN: Azobisisobutyronitrile; ABVN: Azobisisoheptanenitrile; MCPMA: Methyl 2-[(2-chloropropionyloxy)methyl]acrylate; DABCO: 1,4-diazabicyclo[2.2.2]octane; DCC: Dicyclohexylcarbodiimide; PMDETA: N , N , N ', N ', N "-Pentamethyldiethylenetriamine; Bpy: 2,2'-Bipyridine; MeTREN: Tris(2-methylaminoethyl)amine; DMSO: Dimethyl sulfoxide; THF: Tetrahydrofuran; DMAP: p-Dimethylaminopyridine.

[0070] The term "C1-C6 alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc.

[0071] To improve the solubility of PEDOT, existing technologies use PSS as a dopant. PSS is a water-soluble polymer with unique properties; its anions, through Coulomb interactions, assist PEDOT in dispersing in aqueous solutions to form a dispersion. However, PSS is insulating, leading to a decrease in the conductivity of the formed PEDOT / PSS film. When used as a cathode material in electronic components such as solid-state capacitors, this increases the capacitor's internal resistance. Under electron microscopy, the PEDOT / PSS in existing technologies forms a core-shell structure, with the core containing PEDOT and the shell containing PSS (which is insulating), thus increasing resistance. Furthermore, dispersions containing PEDOT / PSS tend to aggregate and form precipitates, exhibiting poor stability and resulting in large particles that are difficult to penetrate the micropores of the etched aluminum foil, leading to low capacitance extraction.

[0072] Based on this, a first aspect of the present invention provides a polymer having the structure shown in formula (I), or a stereoisomer, nitride, hydrate, solvate, or salt thereof having the structure shown in formula (I): Equation (I) in: R1 is selected from H and C1-C6 alkyl groups; R2 is selected from F, Cl, Br, and I; x, y, and z are each independently selected from any integer in the range of 2 to 300; "+" indicates a positive charge; "-" indicates a negative charge; " " represents connection to a repeating unit or H; "┈" refers to electrostatic force.

[0073] The polymer (PMCPMA-g-PSS / PEDOT) provided by this invention is the main component in the PEDOT dispersion, which can improve the electrical conductivity and heat resistance of the PEDOT dispersion after film formation.

[0074] According to a specific embodiment of the present invention, R1 is selected from H, methyl, ethyl, and tert-butyl; R2 is selected from Cl and Br; x is selected from 2-200; preferably 2-150; preferably 5-100; preferably 10-80; preferably 10-50; y is selected from 2-200; preferably 2-150; preferably 2-100; preferably 2-50; more preferably 2-30; z is selected from 2-200.

[0075] Therefore, the dispersion prepared by the polymer can improve the conductivity and heat resistance of the PEDOT dispersion after film formation. When applied to capacitors, it can help reduce capacitor resistance, increase capacitor capacitance extraction rate, and ultimately improve capacitor lifespan.

[0076] According to a specific embodiment of the present invention, the polymer has the following structural formula: (I-1) (I-2) (I-3) or (I-4).

[0077] According to an embodiment of the present invention, a second aspect of the present invention provides a PEDOT dispersion comprising the polymer described in the first aspect and the EDOT monomer.

[0078] The PEDOT dispersion provided in this application is a dark blue mixture. This dark blue mixture has good stability, and after being formed into a film, it exhibits good electrical conductivity.

[0079] According to a specific embodiment of the present invention, the mass ratio of the polymer to the EDOT monomer in the PEDOT dispersion is (20-50):(1-20). As some specific examples, the mass ratio of the polymer to the EDOT monomer in the PEDOT dispersion can be 20:1, 30:1, 40:1, 50:1, 20:10, 30:10, 40:10, 50:10, 20:20, 30:20, 40:20, 50:20, etc., preferably (30-50):(1-10).

[0080] According to a specific embodiment of the present invention, the PEDOT dispersion further includes water and dimethyl sulfoxide, and the mass ratio of the polymer, EDOT monomer, dimethyl sulfoxide and water in the PEDOT dispersion is (20-50):(1-20):(50-200):(200-500). As some specific examples, the mass ratio of the polymer, EDOT monomer, dimethyl sulfoxide and water in the PEDOT dispersion can be 20:1:50:200, 30:10:100:400, 50:20:200:500, etc., preferably (30-50):(1-10):(100-200):(200-400).

[0081] According to specific embodiments of the present invention, the solid content of the PEDOT dispersion is 1%-15%. As some specific examples, the solid content of the PEDOT dispersion may be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., preferably 1%-10%, more preferably 4%-8%. Specifically, the meaning of solid content is known in the art, and the method for testing solid content can be a conventional method in the art.

[0082] According to embodiments of the present invention, a third aspect provides a method for preparing a PEDOT dispersion, comprising the following steps: The polymer PMCPMA-g-PSS is reacted with EDOT monomer to obtain a mixture containing the polymer described in the first aspect or the PEDOT dispersion described in the second aspect. The polymer PMCPMA-g-PSS has the structure shown in formula (II): Equation (II), R1, R2, x, y are as described in the first aspect.

[0083] The method provided by this invention can be used to prepare the PEDOT dispersion, which exhibits good electrical conductivity and heat resistance. Furthermore, the method provided by this invention utilizes controlled free radical polymerization to obtain segments with precise molecular weights, effectively solving the problem that existing technologies cannot obtain target products with well-defined structures and controllable molecular weights.

[0084] According to a specific embodiment of the present invention, the method further includes: The polymer PMCPMA-g-PSS, EDOT monomer, oxidant, first catalyst and pH adjuster are mixed to carry out the first reaction to obtain a mixture.

[0085] According to a specific embodiment of the present invention, the mass ratio of the EDOT monomer to the polymer PMCPMA-g-PSS is (1-10):(1-20). As some specific examples, the mass ratio of the EDOT monomer to the polymer PMCPMA-g-PSS is 1:1, 5:1, 10:1, 1:5, 1:10, 1:15, 1:20, etc., preferably (1-10):(1-15), preferably (1-10):(1-10), preferably (1-5):(1-10), and more preferably (1-5):(1-5).

[0086] According to a specific embodiment of the present invention, the molar ratio of the oxidant to the EDOT monomer is (0.3-3):1. As some specific examples, the molar ratio of the oxidant to the EDOT monomer can be 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, etc., preferably (0.3-2):1, and more preferably (0.3-1):1. If too much oxidant is used, it may cause side reactions, reduce the purity of the product, and increase the impurity content; if too little oxidant is used, oxidation cannot be sufficient.

[0087] According to specific embodiments of the present invention, the type of oxidant is not particularly limited. As some specific examples, the oxidant includes at least one of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0088] According to a specific embodiment of the present invention, the molar ratio of the first catalyst to the EDOT monomer is (0.001-0.006):1. As some specific examples, the molar ratio of the first catalyst to the EDOT monomer can be 0.001:1, 0.002:1, 0.003:1, 0.004:1, 0.005:1, 0.006:1, etc., preferably (0.001-0.005):1, more preferably (0.001-0.004):1, and more preferably (0.001-0.003):1. Therefore, the first catalyst can catalyze the reaction to proceed fully without increasing cost or impurity content.

[0089] According to specific embodiments of the present invention, the type of the first catalyst is not particularly limited. As some specific examples, the first catalyst includes, but is not limited to, ferric sulfate. Specifically, ferric sulfate does not corrode the electrode foil of the capacitor.

[0090] According to specific embodiments of the present invention, the type of pH adjuster is not particularly limited, and some specific examples include, but are not limited to, acetic acid. Specifically, a pH adjuster is used to maintain the pH of the dispersion between 2 and 5 to improve the conductivity of the dispersion after film formation.

[0091] According to a specific embodiment of the present invention, the temperature of the first reaction is 10 ℃-40 ℃. As some specific examples, the temperature of the first reaction can be 10 ℃, 20 ℃, 30 ℃, 40 ℃, etc., preferably 20 ℃-30 ℃. Thus, the reaction can proceed fully.

[0092] According to a specific embodiment of the present invention, the first reaction time is 15 h-30 h. As some specific examples, the first reaction time can be 15 h, 20 h, 25 h, 30 h, etc. Thus, the reaction can proceed sufficiently.

[0093] According to an embodiment of the present invention, the first reaction is carried out in a mixed solvent of dimethyl sulfoxide and water.

[0094] According to a specific embodiment of the present invention, the solvent of the mixture includes dimethyl sulfoxide and water.

[0095] According to specific embodiments of the present invention, the molar ratio of dimethyl sulfoxide to water is 1:(2-20). As some specific examples, the molar ratio of dimethyl sulfoxide to water may be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, etc.

[0096] According to specific embodiments of the present invention, the mass ratio of the dimethyl sulfoxide to the EDOT monomer is (0.1-10):1. As some specific examples, the mass ratio of the dimethyl sulfoxide to the EDOT monomer can be 0.1:1, 0.2:1, 0.5:1, 1:1, 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.

[0097] Specifically, when ammonium persulfate is used as the oxidant and ferric sulfate as the first catalyst, the preparation method of the PEDOT dispersion can be represented by the following reaction formula:

[0098] According to a specific embodiment of the present invention, the method further includes the following steps for preparing the polymer PMCPMA-g-PSS: The polymer PMCPMA, sodium 4-vinylbenzenesulfonate, a second catalyst, and a ligand are mixed to carry out a second reaction to obtain the polymer PMCPMA-g-PSS. The polymer PMCPMA has the structure shown in formula (Ⅲ): Equation (Ⅲ); R1, R2, x are as described in the first aspect.

[0099] According to a specific embodiment of the present invention, the molar ratio of sodium 4-vinylbenzenesulfonate to the polymer PMCPMA is 1000:(1-300). As some specific examples, the molar ratio of sodium 4-vinylbenzenesulfonate to the polymer PMCPMA can be 50:1, 120:1, 180:1, 240:1, 360:1, 500:1, 600:1, 1000:1, etc.

[0100] According to specific embodiments of the present invention, the molar ratio of the second catalyst to the polymer PMCPMA is (1-300):(1-10). As some specific examples, the molar ratio of the second catalyst to the polymer PMCPMA can be 10:1, 16:1, 20:1, 30:1, 40:1, 50:1, etc. Therefore, the second catalyst can catalyze the reaction to proceed fully without increasing cost or impurity content.

[0101] According to specific embodiments of the present invention, the type of the second catalyst is not particularly limited. As some specific examples, the second catalyst includes at least one of cuprous bromide, cuprous chloride, and cuprous sulfate. Therefore, the copper catalyst exhibits good catalytic effect for the second reaction.

[0102] According to specific embodiments of the present invention, the molar ratio of the ligand to the polymer PMCPMA is (1-300):(1-10). As some specific examples, the molar ratio of the ligand to the polymer PMCPMA can be 10:1, 16:1, 20:1, 30:1, 40:1, 50:1, etc.

[0103] According to specific embodiments of the present invention, the type of ligand is not particularly limited; as some specific examples, the ligand includes N , N , N ', N ', NAt least one of '-pentamethyldiethylenetriamine (PMDETA), 2,2'-bipyridine (bpy), and tris(2-methylaminoethyl)amine (MeTREN).

[0104] According to a specific embodiment of the present invention, the temperature of the second reaction is 30°C-80°C. As some specific examples, the temperature of the second reaction can be 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, etc. Therefore, the reaction can proceed fully.

[0105] According to a specific embodiment of the present invention, the second reaction time is 2 h-30 h. As some specific examples, the second reaction time can be 2 h, 5 h, 10 h, 20 h, 30 h, etc. Thus, the reaction can proceed fully.

[0106] According to a specific embodiment of the present invention, the second reaction is carried out under anaerobic conditions.

[0107] According to an embodiment of the present invention, the second reaction is carried out in the presence of tetrahydrofuran.

[0108] According to a specific embodiment of the present invention, the specific operation for preparing the polymer PMCPMA-g-PSS is as follows: dissolve the monomer sodium 4-vinylbenzenesulfonate (SSNa) in tetrahydrofuran (THF), add the polymer PMCPMA and a second catalyst, seal to remove oxygen, add the ligand, and then react at 30 ℃-80 ℃ for 2 h-30 h to obtain the polymer PMCPMA-g-PSS.

[0109] Specifically, the monomer sodium 4-vinylbenzenesulfonate can be dissolved in preheated tetrahydrofuran. The preheating temperature can be 30 ℃-60 ℃.

[0110] According to a specific embodiment of the present invention, the method further includes the following steps for preparing the polymer PMCPMA: The intermediate is obtained by reacting acrylate with formaldehyde. The intermediate was reacted with 2-halopropionic acid to obtain the monomer MCPMA; The monomer MCPMA, chain transfer agent, and initiator are subjected to RAFT polymerization to obtain the polymer PMCPMA; The monomer MCPMA has the structure shown in formula (Ⅳ): Equation (Ⅳ), where R1 and R2 are as described in the first aspect.

[0111] According to specific embodiments of the present invention, the type of acrylate is not particularly limited. As some specific examples, the acrylate includes one of methyl acrylate, ethyl acrylate, and tert-butyl acrylate.

[0112] According to embodiments of the present invention, the molar ratio of acrylate to formaldehyde is (1-5):(1-5); as some specific examples, the molar ratio of acrylate to formaldehyde is 1:1, 2:1, 3:1, 4:1, 5:1, 1:2, 3:2, 5:2, 1:3, 2:3, 4:3, 5:3, 1:4, 3:4, 5:4, 1:5, 2:5, 3:5, 4:5, 5:5, etc.

[0113] According to an embodiment of the present invention, the reaction of the acrylate with formaldehyde is carried out in a mixed solvent of THF and deionized water, wherein the THF and deionized water have the same volume.

[0114] According to a specific embodiment of the present invention, during the reaction of the acrylate with formaldehyde, 1,4-diazabicyclo[2.2.2]octane (DABCO) and a base may be added, wherein 1,4-diazabicyclo[2.2.2]octane (DABCO) acts as a catalyst in the reaction, and the base includes triethylamine for dehydrogenation. The molar ratio of the acrylate to 1,4-diazabicyclo[2.2.2]octane (DABCO) is (0.5-5):1. As some specific examples, the molar ratio of the acrylate to 1,4-diazabicyclo[2.2.2]octane (DABCO) is 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, etc. The molar ratio of acrylate to triethylamine is (0.05-0.5):1. As some specific examples, the molar ratio of acrylate to triethylamine is 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, etc.

[0115] According to embodiments of the present invention, the reaction temperature of the acrylate with formaldehyde is 20 ℃-30 ℃. As some specific examples, the reaction temperature of the acrylate with formaldehyde is 20 ℃, 25 ℃, 30 ℃, etc.; the reaction time is 1 h-5 h. As some specific examples, the reaction time of the acrylate with formaldehyde is 1 h, 2 h, 3 h, 4 h, 5 h, etc.

[0116] According to an embodiment of the present invention, the acrylate reacts with formaldehyde at 20 ℃-30 ℃ for 1 h-5 h, and then the temperature is raised to 50 ℃-70 ℃ for another 20 h-30 h.

[0117] According to specific embodiments of the present invention, the type of 2-halopropionic acid is not particularly limited. As some specific examples, the 2-halopropionic acid includes one of 2-chloropropionic acid and 2-bromopropionic acid.

[0118] According to embodiments of the present invention, the molar ratio of the intermediate to 2-halopropionic acid is (1-5):(1-5); as some specific examples, the molar ratio of the intermediate to 2-halopropionic acid is 1:1, 2:1, 3:1, 4:1, 5:1, 1:2, 3:2, 5:2, 1:3, 2:3, 4:3, 5:3, 1:4, 3:4, 5:4, 1:5, 2:5, 3:5, 4:5, 5:5, etc.

[0119] According to a specific embodiment of the present invention, during the reaction of the intermediate with 2-halopropionic acid, dicyclohexylcarbodiimide (DCC) can be added as a dehydrating condensing agent and p-dimethylaminopyridine (DMAP) as a catalyst to promote the reaction.

[0120] According to embodiments of the present invention, the molar ratio of p-dimethylaminopyridine (DMAP) to the intermediate is (0.01-0.1):1. As specific examples, the molar ratio of p-dimethylaminopyridine (DMAP) to the intermediate is 0.01:1, 0.05:1, 0.1:1, etc. N- The molar ratio of cyclohexylsuccinimide (DCC) to the intermediate is (0.5-1.5):1. As some specific examples, the... N- The molar ratio of cyclohexylsuccinimide (DCC) to the intermediate is 0.5:1, 1:1, 1.5:1, etc.

[0121] According to embodiments of the present invention, the reaction temperature of the intermediate with 2-halopropionic acid is -5 ℃ to 0 ℃. As some specific examples, the reaction temperature of the intermediate with 2-halopropionic acid is -5 ℃, -3 ℃, 0 ℃, etc.; the reaction time is 1 h to 24 h. As some specific examples, the reaction time of the intermediate with 2-halopropionic acid is 1 h, 5 h, 10 h, 15 h, 20 h, 24 h, etc.

[0122] According to specific embodiments of the present invention, the type of solvent used in preparing the monomer MCPMA is not particularly limited. Some specific examples include at least one of water, n-hexane, chloromethane, dichloromethane, trichloromethane, tetrahydrofuran, and toluene.

[0123] According to specific embodiments of the present invention, the type of chain transfer agent is not particularly limited, and as some specific examples, it includes, but is not limited to, isopropyl phenyl dithiobenzoate (CDB).

[0124] According to embodiments of the present invention, the molar ratio of the chain transfer agent to the monomer MCPMA is (0.01-0.1):1. As some specific examples, the molar ratio of the chain transfer agent to the monomer MCPMA is 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, etc.

[0125] According to specific embodiments of the present invention, the type of initiator is not particularly limited. As some specific examples, the initiator includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate.

[0126] According to embodiments of the present invention, the molar ratio of the initiator to the monomer MCPMA is (0.01-0.05):1. As some specific examples, the molar ratio of the chain transfer agent to the monomer MCPMA is 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, etc.

[0127] According to specific embodiments of the present invention, the temperature of the RAFT polymerization reaction is 50°C-90°C. As some specific examples, the temperature of the RAFT polymerization reaction can be 50°C, 60°C, 70°C, 80°C, 90°C, etc. Therefore, the reaction can proceed fully.

[0128] According to specific embodiments of the present invention, the RAFT polymerization reaction takes 10-30 hours. As some specific examples, the RAFT polymerization reaction can take 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, etc. Therefore, the reaction can proceed sufficiently.

[0129] According to specific embodiments of the present invention, the type of solvent used in the RAFT polymerization reaction is not particularly limited. Specific examples include at least one of tetrahydrofuran, monochloroethane, dichloromethane, trichloromethane, and toluene, with toluene being preferred. Specifically, the monomer MCPMA is readily soluble in toluene, and toluene has a high boiling point, which meets the reaction temperature requirements.

[0130] Specifically, when AIBN is used as the initiator, CDB as the chain transfer agent, cuprous bromide as the second catalyst, and PMDETA as the ligand, the synthetic route of the polymer PMCPMA-g-PSS is shown in the following reaction formula:

[0131] According to embodiments of the present invention, a fourth aspect provides a polymer PMCPMA-g-PSS having the structure shown in formula (II), or a stereoisomer, nitride, hydrate, solvate, or salt thereof having the structure shown in formula (II): Equation (II), where R1, R2, x, and y are as described in the first aspect.

[0132] The polymer PMCPMA-g-PSS provided by this invention is an amphiphilic graft copolymer that can be used to prepare the aforementioned PEDOT dispersion.

[0133] According to embodiments of the present invention, the fifth aspect of the present invention provides the application of the polymer described in the first aspect, or the PEDOT dispersion described in the second aspect, or the PEDOT dispersion obtained according to the method described in the third aspect, or the polymer PMCPMA-g-PSS described in the fourth aspect, in solid capacitors.

[0134] According to a specific embodiment of the present invention, the solid capacitor can be prepared by immersing the wound capacitor core in the PEDOT dispersion provided by the present invention, evacuating, pressurizing, drying, repeating this process three or more times, and assembling the capacitor. The assembled solid capacitor has dimensions of φ10×13mm and a specification of 25V 560μF.

[0135] The present invention will be explained below with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0136] Example 1 This embodiment provides a PEDOT dispersion and its preparation method, including the following steps: (1) Preparation of monomer MCPMA Methyl acrylate (0.33 mol), formaldehyde aqueous solution (formaldehyde aqueous solution: methanol 38 wt%, 0.5 mol formaldehyde), THF (50 mL), deionized water (maintaining equal volumes of THF and water in the system), DABCO (0.033 mol), and triethylamine (0.033 mol) were added to a 500 mL three-necked flask with a pre-placed magnetic inlet. The reaction was carried out at 25 °C for 3 h, and the system became colorless and transparent. After standing, the layers separated. The reaction solution was heated to 55 °C and then stirred for 24 h. After cooling, the layers separated. The aqueous phase was extracted three times with diethyl ether (100 mL × 3). The organic phases were combined, washed three times with saturated brine, and dried overnight with anhydrous magnesium sulfate. The mixture was filtered, concentrated using a rotary evaporator, and hydroquinone was added as a polymerization inhibitor. The fraction collected at 80 °C and 60 Pa was distilled under reduced pressure to obtain 51.6 g of colorless and transparent liquid tert-butyl hydroxymethyl acrylate.

[0137] Add 300 mL of freshly distilled dichloromethane, 0.1 mol of the aforementioned tert-butyl hydroxymethyl acrylate, 0.1 mol of 2-chloropropionic acid, and 0.001 mol of p-dimethylaminopyridine (DMAP) to a 500 mL three-necked flask pre-positioned with a magnetic stir bar. After cooling the solution in an ice-water bath for 1 h, add 0.1 mol of dicyclohexylcarbodiimide (DCC) and stir overnight. Filter to remove the white solid, concentrate the filtrate, and separate by column chromatography (eluting solvent: ethyl acetate and n-hexane (volume ratio 1:6). Concentrate using a rotary evaporator to obtain 23.2 g of a colorless liquid. Its mass spectrometry, infrared spectroscopy, and 1H NMR data are as follows: ESI-MS (m / z), (M+H) + =207; FT-IR, ν / cm -1 : 2977 (ν C–H ), 2936 (ν C–H ), 1752 (ν C=O ), 1723 (ν C=O ), 1646(ν C=C ), 1453, 1391, 1367, 1253, 1151, 1075, 952, 849; 1 H NMR (300 MHz, CDCl3), δ: 1.66 (3H, CH3CH), 3.66 (3H, CH3), 4.38(1H, CH3CH), 4.81 (2H, CO2CH2), 5.80 (1H, CH2=C), 6.26(1H, CH2=C).

[0138] (2) Preparation of polymer PMCPMA Add AIBN (0.4 mmol) and CDB (1.2 mmol) to a 100 mL flask with a pre-placed magnetic magnet. After purging with nitrogen three times, add the monomer MCPMA (30 mmol) obtained in step (1) and freshly distilled toluene (5.0 mL). After three cycles of freezing, vacuuming, thawing, dissolving, and purging with nitrogen, react in a stable 70 °C oil bath for 24 h and then quench. The product is then diluted with THF and precipitated three times in n-hexane. After filtration and vacuum drying overnight, 2.61 g of pink solid is obtained. End-group removal: 2.6 g of the dried pink solid (0.60 mmol dithioester end group), AIBN (6.0 mmol), and freshly distilled toluene (100 mL) were added to a 250 mL three-necked flask with a pre-placed magnetic magnet. The system was pink. The reaction was stopped at 80 °C for 8 h, at which point the system was colorless and transparent. After concentration using a rotary evaporator, the solid was precipitated three times in n-hexane and dried under vacuum overnight. 2.17 g of white powdery solid was obtained. The molecular weight of the obtained white powdery solid, determined by gel permeation chromatography (GPC), was Mn = 4100 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.09; where Mn is the number-average molecular weight and Mw is the weight-average molecular weight.

[0139] (3) Preparation of polymer PMCPMA(4100)-g-PSS(20600) The monomer SSNa (30 mmol) was dissolved in 200 mL of THF at 60 °C, cooled to room temperature, and then the polymer PMCPMA (Mn = 4100 g·mol⁻¹) obtained in step (2) was added. -1 0.25 mmol of PMDETA and 5.0 mmol of cuprous bromide were added to the flask. The flask was sealed and purged three times with N2 for 10 minutes to remove oxygen. Then, 10 mL of a THF solution of 5.0 mmol of PMDETA was added through a gas-tight syringe. After three cycles of freezing-pumping-thawing to remove oxygen, the mixture was heated to 70 °C and reacted for 24 h. The polymerization was then terminated by transferring the mixture to liquid nitrogen. The reaction mixture was diluted with THF and residual cuprous bromide was removed by passing it through an alumina column. After concentration, the mixture was precipitated in methanol and dried at 60 °C for 12 h to obtain 6.29 g of polymer PMCPMA(4100)-g-PSS(20600). The molecular weight of the polymer was determined by GPC to be Mn = 24800 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.28.

[0140] (4) Preparation of PMCPMA(4100)-g-PSS(20600) / PEDOT dispersion PMCPMA(4100)-g-PSS(20600) (Mn = 24800 g·mol⁻¹) -1 0.25 mmol) was dissolved in 70 mL of dimethyl sulfoxide and slowly added to 180 mL of deionized water. Acetic acid (2.5 mL, analytical grade, 99.5%), monomer EDOT (50.0 mmol), oxidant ammonium persulfate (35 mmol), and catalyst ferric sulfate (0.13 mmol) were added. After reacting at room temperature for 20 h, a PMCPMA(4100)-g-PSS(20600) / PEDOT dispersion with a solid content of 4.35% was obtained.

[0141] (5) Fabrication of capacitors The wound capacitor core was immersed in the PMCPMA(4100)-g-PSS(20600) / PEDOT dispersion obtained above, and subjected to vacuuming at 0.1 MPa for 10 minutes, pressurizing at 0.1 MPa for 10 minutes, and drying at 130 ℃ for 1 h, repeated three times. The resulting solid capacitor was assembled using an assembly machine into a φ10×13mm solid capacitor with a specification of 25V 560μF.

[0142] Example 2 This embodiment provides a PEDOT dispersion and its preparation method, including the following steps: (1) Preparation of monomer MCPMA The preparation process is the same as in Example 1.

[0143] (2) Preparation of polymer PMCPMA The preparation process is the same as in Example 1.

[0144] (3) Preparation of polymer PMCPMA(4100)-g-PSS(41300) The monomer SSNa (60 mmol) was dissolved in 200 mL of THF at 60 °C, cooled to room temperature, and then the polymer PMCPMA (Mn = 4100 g·mol⁻¹) obtained in step (2) was added. -10.25 mmol) of PMDETA and 5.0 mmol of cuprous bromide were added to the flask. The flask was sealed and purged three times with N2 for 10 minutes to remove oxygen. Then, 10 mL of THF solution containing 5.0 mmol of PMDETA was added through a gas-tight syringe. After deoxygenation of the flask by three freeze-pump-thaw cycles, the temperature was raised to 70 °C and reacted for 24 h. The polymerization was then terminated by transferring the flask to liquid nitrogen. The reaction mixture was diluted with THF and residual cuprous bromide was removed by passing it through an alumina column. After concentration, the precipitate was formed in methanol and dried at 60 °C for 12 h to obtain 11.45 g of polymer PMCPMA(4100)-g-PSS(41300). The molecular weight was determined by GPC to be Mn = 45400 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.36.

[0145] (4) Preparation of PMCPMA(4100)-g-PSS(41300) / PEDOT dispersion PMCPMA(4100)-g-PSS(41300) (Mn = 45400 g·mol⁻¹) -1 0.25 mmol) was dissolved in 70 mL of dimethyl sulfoxide and slowly added to 180 mL of deionized water. Acetic acid (2.5 mL, analytical grade, 99.5%), monomer EDOT (50.0 mmol), oxidant ammonium persulfate (35 mmol), and catalyst ferric sulfate (0.13 mmol) were added. After reacting at room temperature for 20 h, a PMCPMA(4100)-g-PSS(41300) / PEDOT dispersion with a solid content of 6.95% was obtained.

[0146] (5) Fabrication of capacitors The wound capacitor core was immersed in the PMCPMA(4100)-g-PSS(41300) / PEDOT dispersion obtained above, and subjected to vacuuming at 0.1 MPa for 10 minutes, pressurizing at 0.1 MPa for 10 minutes, and drying at 130 ℃ for 1 h, repeated three times. The resulting solid capacitor was assembled using an assembly machine into a φ10×13mm solid capacitor with a specification of 25V 560μF.

[0147] Example 3 This embodiment provides a PEDOT dispersion and its preparation method, including the following steps: (1) Preparation of monomer MCPMA The preparation process is the same as in Example 1.

[0148] (2) Preparation of polymer PMCPMA Add AIBN (0.67 mmol) and CDB (2.0 mmol) to a 100 mL flask with a pre-placed magnetic magnet. After purging with nitrogen three times, add the monomer MCPMA (50 mmol) obtained in step (1) and freshly distilled toluene (8.5 mL). After three cycles of freezing, vacuuming, thawing, dissolving, and purging with nitrogen, react in a stable 70 °C oil bath for 24 h and then quench. The product is then diluted with THF and precipitated three times in n-hexane. After filtration and vacuum drying overnight, 2.61 g of pink solid is obtained. End-group removal: 2.6 g of the dried pink solid (1.00 mmol dithioester end group), AIBN (10.0 mmol), and freshly distilled toluene (100 mL) were added to a 250 mL three-necked flask with a pre-placed magnetic flask. The system was pink. The reaction was stopped at 80 °C for 8 h, at which point the system was colorless and transparent. The mixture was concentrated using a rotary evaporator, precipitated three times in n-hexane, and dried under vacuum overnight. 3.63 g of white powdery solid was obtained. The molecular weight of the white powdery solid was determined by GPC to be Mn = 6200 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.12.

[0149] (3) Preparation of polymer PMCPMA(6200)-g-PSS(30900) The monomer SSNa (45 mmol) was dissolved in 200 mL of THF at 60 °C, cooled to room temperature, and then the polymer PMCPMA (Mn = 6200 g·mol⁻¹) obtained in step (2) was added. -1 0.25 mmol) of PMDETA and 8.0 mmol of cuprous bromide were added to the flask. The flask was sealed and purged three times with N2 for 10 minutes to remove oxygen. Then, 10 mL of a THF solution of PMDETA (8.0 mmol) was added through a gas-tight syringe. After three freeze-pump-thaw cycles to remove oxygen, the mixture was heated to 70 °C and reacted for 24 h. The polymerization was then terminated by transferring the mixture to liquid nitrogen. The reaction mixture was diluted with THF and residual cuprous bromide was removed by passing it through an alumina column. After concentration, the mixture was precipitated in methanol and dried at 60 °C for 12 h to obtain 9.32 g of polymer PMCPMA(6200)-g-PSS(30900). The molecular weight of the polymer was determined by GPC to be Mn = 37100 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.25.

[0150] (4) Preparation of PMCPMA(6200)-g-PSS(30900) / PEDOT dispersion PMCPMA(6200)-g-PSS(30900) (Mn = 37100 g·mol⁻¹) -10.25 mmol) was dissolved in 70 mL of dimethyl sulfoxide and slowly added to 180 mL of deionized water. Acetic acid (2.5 mL, analytical grade, 99.5%), monomer EDOT (50.0 mmol), oxidant ammonium persulfate (35 mmol), and catalyst ferric sulfate (0.13 mmol) were added. After reacting at room temperature for 20 h, a PMCPMA(6200)-g-PSS(30900) / PEDOT dispersion with a solid content of 5.98% was obtained.

[0151] (5) Fabrication of capacitors The wound capacitor core was immersed in the PMCPMA(6200)-g-PSS(30900) / PEDOT dispersion obtained above, and subjected to vacuuming at 0.1 MPa for 10 minutes, pressurizing at 0.1 MPa for 10 minutes, and drying at 130 ℃ for 1 h, repeated three times. The resulting solid capacitor was assembled using an assembly machine into a φ10×13mm solid capacitor with a specification of 25V 560μF.

[0152] Example 4 This embodiment provides a PEDOT dispersion and its preparation method, including the following steps: (1) Preparation of monomer MCPMA The preparation process is the same as in Example 1.

[0153] (2) Preparation of polymer PMCPMA Add AIBN (0.67 mmol) and CDB (2.0 mmol) to a 100 mL flask with a pre-placed magnetic magnet. After purging with nitrogen three times, add the monomer MCPMA (50 mmol) obtained in step (1) and freshly distilled toluene (8.5 mL). After three cycles of freezing, vacuuming, thawing, dissolving, and purging with nitrogen, react in a stable 70 °C oil bath for 24 h and then quench. The product is then diluted with THF and precipitated three times in n-hexane. After filtration and vacuum drying overnight, 2.61 g of pink solid is obtained. End-group removal: 2.6 g of the dried pink solid (1.00 mmol dithioester end group), AIBN (10.0 mmol), and freshly distilled toluene (100 mL) were added to a 250 mL three-necked flask with a pre-placed magnetic flask. The system was pink. The reaction was stopped at 80 °C for 8 h, at which point the system was colorless and transparent. The mixture was concentrated using a rotary evaporator, precipitated three times in n-hexane, and dried under vacuum overnight. 3.63 g of white powdery solid was obtained. The molecular weight of the white powdery solid was determined by GPC to be Mn = 6200 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.12.

[0154] (3) Preparation of polymer PMCPMA(6200)-g-PSS(61800) The monomer SSNa (90 mmol) was dissolved in 200 mL of THF at 60 °C, cooled to room temperature, and then the polymer PMCPMA (Mn = 6200 g·mol⁻¹) obtained in step (2) was added. -1 0.25 mmol) of PMDETA and 8.0 mmol of cuprous bromide were added to the flask. The flask was sealed and purged three times with N2 for 10 minutes to remove oxygen. Then, 10 mL of a THF solution of PMDETA (8.0 mmol) was added through a gas-tight syringe. After deoxygenation of the flask by three freeze-pump-thaw cycles, the temperature was raised to 70 °C and reacted for 24 h. The polymerization was then terminated by transferring the flask to liquid nitrogen. The reaction mixture was diluted with THF and residual cuprous bromide was removed by passing it through an alumina column. After concentration, the precipitate was precipitated in methanol and dried at 60 °C for 12 h to obtain 17.01 g of polymer PMCPMA(6200)-g-PSS(61800). The molecular weight was determined by GPC to be Mn = 68000 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.39.

[0155] (4) Preparation of PMCPMA(6200)-g-PSS(61800) / PEDOT dispersion PMCPMA(6200)-g-PSS(61800) (Mn = 68000 g·mol⁻¹) -1 0.125 mmol) was dissolved in 70 mL of dimethyl sulfoxide and slowly added to 180 mL of deionized water. Acetic acid (2.5 mL, analytical grade, 99.5%), monomer EDOT (50.0 mmol), oxidant ammonium persulfate (35 mmol), and catalyst ferric sulfate (0.13 mmol) were added. After reacting at room temperature for 20 h, a PMCPMA(6200)-g-PSS(61800) / PEDOT dispersion with a solid content of 6.38% was obtained.

[0156] (5) Fabrication of capacitors The wound capacitor core was immersed in the PMCPMA(6200)-g-PSS(61800) / PEDOT dispersion obtained above, and subjected to vacuuming at 0.1 MPa for 10 minutes, pressurizing at 0.1 MPa for 10 minutes, and drying at 130 ℃ for 1 h, repeated three times. The resulting solid capacitor was assembled using an assembly machine into a φ10×13mm solid capacitor with a specification of 25V 560μF.

[0157] Comparative Example 1 In this comparative example, PEDOT dispersions were prepared using PSS(20000) synthesized by conventional free radical polymerization as a template. The specific steps are as follows: (1) The monomer SSNa (120 mmol) was dissolved in 500 mL of THF at 60 °C. After cooling to room temperature, 1.0 mmol of ethyl 2-bromoacetate and 1.0 mmol of cuprous bromide were added. The flask was sealed and purged with N2 three times for 10 minutes to remove oxygen. Then, 10 mL of a THF solution containing 1.0 mmol of PMDETA was added through a gas-tight syringe. The flask was deoxygenated by three freeze-pump-thaw cycles. After reacting at 70 °C for 24 h, the reaction mixture was transferred to liquid nitrogen to terminate the polymerization. The reaction mixture was diluted with THF and residual cuprous bromide was removed by passing it through an alumina column. After concentration, the mixture was precipitated in methanol and dried at 60 °C for 12 h to obtain the product PSS (20000). The molecular weight was determined by GPC to be Mn = 20000 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.25.

[0158] (2) PSS (Mn = 20000 g·mol -1 1.00 mmol) was added to a mixed solvent of dimethyl sulfoxide and deionized water (500 mL, DMSO to deionized water molar ratio of 1:11), acetic acid (5.0 mL, analytical grade, 99.5%), monomer EDOT (141 mmol), oxidant ammonium persulfate (70 mmol), and catalyst ferric sulfate (0.26 mmol). After reacting at room temperature for 20 h, PSS(20000):PEDOT dispersion was obtained.

[0159] (3) Immerse the wound capacitor core in the PSS(20000):PEDOT dispersion obtained above, vacuum at 0.1MPa for 10 minutes, pressurize at 0.1MPa for 10 minutes, and dry at 130 ℃ for 1 h. Repeat this process three times. Assemble the capacitor core into a solid capacitor with dimensions of φ10×13mm and specifications of 25V560μF using an assembly machine.

[0160] Comparative Example 2 In this comparative example, PEDOT dispersions were prepared using PSS(40000) synthesized by conventional free radical polymerization as a template. The specific steps are as follows: (1) The monomer SSNa (240 mmol) was dissolved in 800 mL of THF at 60 °C. After cooling to room temperature, 1.0 mmol of ethyl 2-bromoacetate and 1.0 mmol of cuprous bromide were added. The flask was sealed and purged with N2 three times for 10 minutes to remove oxygen. Then, 10 mL of a THF solution containing 1.0 mmol of PMDETA was added through a gas-tight syringe. The flask was deoxygenated by three freeze-pump-thaw cycles. After reacting at 70 °C for 24 h, the reaction mixture was transferred to liquid nitrogen to terminate the polymerization. The reaction mixture was diluted with THF and residual cuprous bromide was removed by passing it through an alumina column. After concentration, the mixture was precipitated in methanol and dried at 60 °C for 12 h to obtain the product PSS (40000). The molecular weight was determined by GPC to be Mn = 40000 g·mol⁻¹. -1 The dispersion is Mw / Mn = 1.37.

[0161] (2) PSS (Mn = 40000 g·mol -1 0.50 mmol) was added to a mixed solvent of dimethyl sulfoxide and deionized water (500 mL, DMSO to deionized water molar ratio of 1:11), acetic acid (5.0 mL, analytical grade, 99.5%), monomer EDOT (141 mmol), oxidant ammonium persulfate (70 mmol), and catalyst ferric sulfate (0.26 mmol). After reacting at room temperature for 20 h, a PSS(40000):PEDOT dispersion was obtained.

[0162] (3) Immerse the wound capacitor core in the PSS(40000):PEDOT dispersion obtained above, vacuum at 0.1MPa for 10 minutes, pressurize at 0.1MPa for 10 minutes, and dry at 130 ℃ for 1 h. Repeat this process three times. Assemble the capacitor core into a solid capacitor with dimensions of φ10×13mm and specifications of 25V560μF using an assembly machine.

[0163] Test case (1) Conductivity test The PEDOT dispersions obtained in Examples 1-4 and Comparative Examples 1-2 were spin-coated into thin films, cut into 10cm × 10cm pieces, and their conductivity was measured using a four-probe tester. The films were then stored in ovens at 20℃, 150℃, and 160℃ for 24 h, and their conductivity was measured afterward; the values ​​were read directly from the instrument. The conductivity of Examples 1-4 and Comparative Examples 1-2 is shown in Table 1.

[0164] Table 1

[0165] Results Analysis: As shown in Table 1, the conductivity of the PEDOT dispersion prepared using the amphiphilic graft copolymer PMCPMA-g-PSS as a template was significantly improved in the examples. Furthermore, the rate of change in conductivity was small at 150 ℃ and 160 ℃, indicating that the conductivity retention was good at high temperatures.

[0166] (2) Parameter testing of capacitors The capacitors prepared in Examples 1-4 and Comparative Examples 1-2 were tested using an LCR bridge tester. The capacitance C, loss tgδ, equivalent series resistance ESR, and impedance Z can be read directly from the instrument. The capacitance extraction rate is calculated as (C / C0)*100% (C is the capacitance, C0 is the capacitance of the anode foil in the core package, and the capacitance can be controlled by controlling the length of the anode foil. In this patent, C0 is 600 μF). The results are shown in Table 2.

[0167] Table 2

[0168] Results Analysis: As shown in Table 2, the solid capacitor prepared by the PEDOT dispersion system using the amphiphilic graft copolymer PMCPMA-g-PSS as a template in the examples has significantly reduced resistance and a high capacitance extraction rate, which can effectively improve the performance of the capacitor.

[0169] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0170] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A polymer, characterized in that, The polymer has the structure shown in Formula (I), or a stereoisomer, nitride, hydrate, solvate, or salt thereof having the structure shown in Formula (I): Equation (I) in: R1 is selected from H and C1-C6 alkyl groups; R2 is selected from F, Cl, Br, and I; x, y, and z are each independently selected from any integer in the range of 2 to 300; "+" indicates a positive charge; "-" indicates a negative charge; " " represents connection with repeating units or H; "┈" refers to electrostatic force.

2. The polymer according to claim 1, characterized in that, R1 is selected from H, methyl, ethyl, and tert-butyl; R2 is selected from Cl and Br; x is selected from 2-200; preferably 2-150; preferably 5-100; preferably 10-80; more preferably 10-50; y is selected from 2-200; preferably 2-150; preferably 2-100; preferably 2-50; more preferably 2-30; z is selected from 2-200; Optionally, the polymer has the following structural formula: (I-1) (I-2) (I-3) or (I-4).

3. A PEDOT dispersion, characterized in that, The PEDOT dispersion comprises the polymer and EDOT monomer as described in claim 1 or 2.

4. The PEDOT dispersion according to claim 3, characterized in that, The mass ratio of the polymer to the EDOT monomer in the PEDOT dispersion is (20-50):(1-20), preferably (30-50):(1-10); Optionally, the PEDOT dispersion further includes water and dimethyl sulfoxide, wherein the mass ratio of the polymer, EDOT monomer, dimethyl sulfoxide and water in the PEDOT dispersion is (20-50):(1-20):(50-200):(200-500), preferably (30-50):(1-10):(100-200):(200-400); Optionally, the solid content of the PEDOT dispersion is 1%-15%, preferably 1%-10%, and more preferably 4%-8%.

5. A method for preparing a PEDOT dispersion, characterized in that, Includes the following steps: The polymer PMCPMA-g-PSS is subjected to a first reaction with the EDOT monomer to obtain a mixture, wherein the mixture contains the polymer according to any one of claims 1 or 2 or the PEDOT dispersion according to any one of claims 3 or 4; The polymer PMCPMA-g-PSS has the structure shown in formula (II): Formula (II), R1, R2, x, y as described in any one of claims 1 or 2.

6. The method according to claim 5, characterized in that, The method further includes: The polymer PMCPMA-g-PSS, EDOT monomer, oxidant, first catalyst and pH adjuster are mixed to carry out the first reaction to obtain a mixture. Optionally, the mass ratio of the EDOT monomer to the polymer PMCPMA-g-PSS is (1-10):(1-20), preferably (1-10):(1-15), more preferably (1-10):(1-10), more preferably (1-5):(1-10), and even more preferably (1-5):(1-5). Optionally, the oxidant includes one or more of ammonium persulfate, potassium persulfate, and sodium persulfate; Optionally, the molar ratio of the oxidant to the EDOT monomer is (0.3-3):1, preferably (0.3-2):1, and more preferably (0.3-1):1; Optionally, the first catalyst comprises ferric sulfate; Optionally, the molar ratio of the first catalyst to the EDOT monomer is (0.001-0.006):1, preferably (0.001-0.005):1, more preferably (0.001-0.004):1, and even more preferably (0.001-0.003):1; Optionally, the temperature of the first reaction is 10 ℃-40 ℃; preferably 20 ℃-30 ℃; Optionally, the duration of the first reaction is 15 h-30 h; Optionally, the pH adjuster includes acetic acid; Optionally, the first reaction is carried out in a mixed solvent of dimethyl sulfoxide and water; Optionally, the molar ratio of the dimethyl sulfoxide to the water is 1:(2-20).

7. The method according to any one of claims 5-6, characterized in that, The method further includes the following steps for preparing the polymer PMCPMA-g-PSS: The polymer PMCPMA, sodium 4-vinylbenzenesulfonate, a second catalyst, and a ligand are mixed to carry out a second reaction to obtain the polymer PMCPMA-g-PSS. The polymer PMCPMA has the structure shown in formula (Ⅲ): Formula (Ⅲ); R1, R2, x as described in any one of claims 1 or 2; Optionally, the molar ratio of sodium 4-vinylbenzenesulfonate to the polymer PMCPMA is 1000:(1-300); Optionally, the molar ratio of the second catalyst to the polymer PMCPMA is (1-300):(1-10); Optionally, the second catalyst includes at least one of cuprous bromide, cuprous chloride, and cuprous sulfate; Optionally, the ligand is N,N,N ' ,N ' ,N One or more of ''-pentamethyldiethylenetriamine, 2,2'-bipyridine, and tris(2-methylaminoethyl)amine; Optionally, the molar ratio of the ligand to the polymer PMCPMA is (1-300):(1-10); Optionally, the second reaction is carried out in the presence of tetrahydrofuran; Optionally, the temperature of the second reaction is 30 ℃-80 ℃; Optionally, the second reaction takes 2 h to 30 h.

8. The method according to claim 7, characterized in that, The method further includes the following steps for preparing the polymer PMCPMA: The intermediate is obtained by reacting acrylate with formaldehyde. The intermediate was reacted with 2-halopropionic acid to obtain the monomer MCPMA; The monomer MCPMA, chain transfer agent, and initiator are subjected to RAFT polymerization to obtain the polymer PMCPMA; The monomer MCPMA has the structure shown in formula (Ⅳ): Formula (Ⅳ); R1, R2 as described in any one of claims 1 or 2; Optionally, the acrylate includes one of methyl acrylate, ethyl acrylate, and tert-butyl acrylate; Optionally, the molar ratio of the acrylate to formaldehyde is (1-5):(1-5); Optionally, the reaction of the acrylate with formaldehyde is carried out in a mixed solvent of THF and deionized water; Optionally, the THF and deionized water have the same volume; Optionally, the reaction of the acrylate with formaldehyde further requires the addition of 1,4-diazabicyclo[2.2.2]octane and a base; Optionally, the base includes triethylamine; Optionally, the reaction temperature of the acrylate with formaldehyde is 20 ℃-30 ℃, and the time is 1 h-5 h; Optionally, the acrylate reacts with formaldehyde at 20 ℃-30 ℃ for 1 h-5 h, then the temperature is raised to 50 ℃-70 ℃ and the reaction continues for another 20 h-30 h; Optionally, the 2-halopropionic acid includes one of 2-chloropropionic acid and 2-bromopropionic acid; Optionally, the molar ratio of the intermediate to 2-halopropionic acid is (1-5):(1-5); Optionally, the reaction of the intermediate with 2-halopropionic acid is carried out in the solvent dichloromethane; Optionally, the reaction of the intermediate with 2-halopropionic acid further requires the addition of p-dimethylaminopyridine and N- Cyclohexylsuccinimide; Optionally, the molar ratio of p-dimethylaminopyridine to the intermediate is (0.01-0.1):1; Optionally, the N- The molar ratio of cyclohexylsuccinimide to the intermediate is (0.5-1.5):1; Optionally, the intermediate reacts with 2-halopropionic acid at a temperature of -5 °C to 0 °C for a time of 1 h to 24 h. Optionally, the chain transfer agent is isopropylphenyl dithiobenzoate; Optionally, the molar ratio of the chain transfer agent to the monomer MCPMA is (0.01-0.1):1; Optionally, the initiator includes at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate; Optionally, the molar ratio of the initiator to the monomer MCPMA is (0.01-0.05):1; Optionally, the temperature of the RAFT polymerization reaction is 50 ℃-90 ℃; Optionally, the RAFT polymerization reaction takes 10 h to 30 h.

9. A polymer PMCPMA-g-PSS, characterized in that, The polymer PMCPMA-g-PSS has the structure shown in Formula (II), or a stereoisomer, nitride, hydrate, solvate, or salt thereof having the structure shown in Formula (II): Formula (II), wherein R1, R2, x, and y are as described in any one of claims 1 or 2.

10. The use of the polymer of claim 1 or 2, or the PEDOT dispersion of claim 3 or 4, or the PEDOT dispersion obtained by the method of any one of claims 5-8, or the polymer PMCPMA-g-PSS of claim 9, in a solid capacitor.

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