High-conductivity polymer compound and preparation method and application of aqueous dispersion liquid of high-conductivity polymer compound

Abstract

The invention discloses a high-conductivity polymer compound and a preparation method and application of a water-based dispersion liquid of the high-conductivity polymer compound. According to the preparation method of the high-conductivity polymer compound aqueous dispersion liquid, long-chain alkyl benzene sulfonic acid is introduced into the compound dispersion liquid containing the pi-conjugated conductive polymer and the polyanion, so that coulomb force between the pi-conjugated conductive polymer and a polyanion chain is weakened; then rapidly intensifying the precipitation of the high-conductivity polymer compound precipitate by using a water-based organic solvent, and finally homogenizing the precipitated high-conductivity polymer compound again under the action of a high-pressure homogenizer to prepare the high-conductivity polymer compound water-based dispersion liquid with excellent stability. The preparation method is simple in process, short in production time, free of heating, low in production cost and beneficial to construction of green production economy.

Description

Technical Field

[0001] The present application relates to conductive polymers, and particularly to a preparation method and application of a highly conductive polymer composite and its aqueous dispersion. Background Art

[0002] As a conductive polymer widely used in the fields of flexible electronic devices, sensors, solar cells, and bioelectronics, π-conjugated conductive polymers have attracted much attention due to their high conductivity, good biocompatibility, and easy solution processability.

[0003] Generally, polyanions are used as dispersants and dopants to improve the dispersion of π-conjugated conductive polymers in water. However, the introduction of polyanions also leads to a decrease in the conductivity of π-conjugated conductive polymers in their aqueous dispersions. In high-performance electronic devices, conductivity is a key factor determining device efficiency. At present, researchers have proposed various strategies to improve the conductivity of aqueous dispersions containing π-conjugated conductive polymers and polyanions. For example, treating π-conjugated conductive polymers or polyanions with dimethyl sulfoxide or ethylene glycol solvents, or doping and modifying π-conjugated conductive polymers or polyanions. However, there are still problems such as high production costs of solvent treatment, the impact of doping modification on their stability, and limited improvement in conductive performance.

[0004] Therefore, there is an urgent need to develop a new improvement strategy for aqueous dispersions containing π-conjugated conductive polymers and polyanions to meet the application requirements of conductive aqueous dispersions in flexible electronic devices and sensors. Summary of the Invention

[0005] Therefore, the technical problem to be solved by the present application is to overcome the above-mentioned defects in the prior art. The purpose is to provide a preparation method of an aqueous dispersion of a highly conductive polymer composite. By introducing long-chain alkylbenzenesulfonic acid into the composite dispersion containing π-conjugated conductive polymers and polyanions, the Coulomb force between the π-conjugated conductive polymers and the polyanion chains is weakened. Subsequently, the precipitation of the highly conductive polymer composite is rapidly accelerated using an aqueous organic solvent. Finally, the precipitated highly conductive polymer composite is re-homogenized under the action of a high-pressure homogenizer to prepare an aqueous dispersion of a highly conductive polymer composite with excellent stability. Moreover, the preparation method has a simple process, a short production time, does not require heating, and has low production costs, which is conducive to the construction of a green production economy.

[0006] In the first aspect of the present application, a preparation method of an aqueous dispersion of a highly conductive polymer composite is provided, including:

[0007] Step 1: Mix the composite dispersion containing π-conjugated conductive polymers and polyanions with long-chain alkylbenzenesulfonic acid, and stir at room temperature for 1 min to 5 min to obtain a gel;

[0008] Step 2: Mix the gel with an aqueous organic solvent and stir for 1 min to 10 min at room temperature to obtain a mixture.

[0009] Step 3: Filter the mixture, take the precipitate and mix it with a solvent, stir for 1 min to 5 min at room temperature, and filter again to obtain a highly conductive polymer composite.

[0010] Step 4: Mix the highly conductive polymer composite with pure water and homogenize it in a high-pressure homogenizer to obtain the aqueous dispersion of the highly conductive polymer composite.

[0011] It is found that in this application, the dispersion of the composite containing the π-conjugated conductive polymer and the polyanion is first mixed with the long-chain alkylbenzenesulfonic acid, and then the aqueous organic solvent is added, and stirred for several minutes at room temperature, and then the precipitate of the highly conductive polymer composite can be obtained, which greatly reduces the processing time and energy loss. Moreover, the aqueous dispersion of the highly conductive polymer composite obtained by homogenizing the highly conductive polymer composite in a high-pressure homogenizer has excellent stability. The surface resistance of the film layer prepared from the aqueous dispersion of the highly conductive polymer composite can be as low as 10 4 Ω / □, greatly broadening its application window.

[0012] In any embodiment, the π-conjugated conductive polymer includes at least one of polypyrrole-based conductive polymers, polythiophene-based conductive polymers, and polyaniline-based conductive polymers, and optionally includes polythiophene-based conductive polymers.

[0013] In any embodiment, the polyanion includes sulfonic polymers and carboxyl compounds, and optionally includes sulfonic polymers.

[0014] In any embodiment, the long-chain alkylbenzenesulfonic acid includes at least one of C 10-16 alkylbenzenesulfonic acids.

[0015] In any embodiment, the solid content of the composite dispersion is 0.5% to 2%.

[0016] In any embodiment, the mass ratio of the composite dispersion to the long-chain alkylbenzenesulfonic acid is (20 to 30):1.

[0017] In any embodiment, the mass ratio of the composite dispersion to the aqueous organic solvent is 1:(1.5 to 3).

[0018] In any embodiment, the solid content of the aqueous dispersion of the highly conductive polymer composite is 0.5% to 1.5%.

[0019] In any embodiment, the average particle size of the aqueous dispersion of the highly conductive polymer composite is 50 nm to 160 nm, optionally 50 nm to 100 nm, and the PI value is 0.3 to 0.5, optionally 0.35 to 0.45.

[0020] In any embodiment, the mixing of the gel with the aqueous organic solvent and stirring at room temperature for 1 min to 10 min to obtain the mixture specifically includes:

[0021] Mix the gel with a first aqueous organic solvent and stir at room temperature for 1 min to 5 min, then add a second aqueous organic solvent and stir at room temperature for 1 min to 5 min to obtain the mixture;

[0022] The first aqueous organic solvent includes at least one of a ketone solvent and an ester solvent, and the second aqueous organic solvent includes an alcohol solvent.

[0023] In any embodiment, the mixing of the gel with the aqueous organic solvent and stirring at room temperature for 1 min to 10 min to obtain the mixture specifically includes:

[0024] Mix the gel with an alcohol solvent and stir at room temperature for 1 min to 5 min to obtain the mixture.

[0025] In any embodiment, the composite dispersion includes at least one of a poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) dispersion, a polypyrrole-poly(styrenesulfonic acid) dispersion, a polyaniline-poly(styrenesulfonic acid) dispersion, a poly(3,4-ethylenedioxythiophene)-poly(vinylsulfonic acid) dispersion, and a poly(3,4-ethylenedioxythiophene)-poly(acrylic acid) dispersion.

[0026] In a second aspect of the present application, a method for preparing a highly conductive polymer composite is provided, including:

[0027] Mix the composite dispersion containing a π-conjugated conductive polymer and a polyanion with a long-chain alkylbenzenesulfonic acid and stir at room temperature for 1 min to 5 min to obtain a gel;

[0028] Mix the gel with an aqueous organic solvent and stir at room temperature for 1 min to 10 min to obtain a mixture;

[0029] Filter the mixture, take the precipitate and mix it with a solvent, stir at room temperature for 1 min to 5 min, and filter again to obtain the highly conductive polymer composite.

[0030] In the third aspect of the present application, an antistatic liquid is provided, which includes a resin, a solvent, an auxiliary agent, and an aqueous dispersion of a highly conductive polymer composite prepared by the preparation method provided in the first aspect of the present application. Based on the total mass of the antistatic liquid, the mass content of the resin is 5% to 10%, the mass content of the solvent is 15% to 35%, the mass content of the auxiliary agent is 0.01% to 5%, and the mass content of the aqueous dispersion of the highly conductive polymer composite is 55% to 80%.

[0031] In the fourth aspect of the present application, an application of the aqueous dispersion of the highly conductive polymer composite prepared by the preparation method provided in the first aspect of the present application in flexible electronic devices and sensors is provided. Specific Embodiments

[0032] Hereinafter, embodiments specifically disclosing the preparation methods and applications of the highly conductive polymer composite and its aqueous dispersion of the present application will be described in detail. However, there may be cases where unnecessary details are omitted. For example, there are cases where details of well-known matters are omitted and repeated descriptions of actually identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the following description is provided for those skilled in the art to fully understand the present application and is not intended to limit the subject matter recited in the claims. Any product that is the same as or similar to the present application obtained by anyone under the inspiration of the present application or by combining the features of the present application with those of other prior arts falls within the protection scope of the present application.

[0033] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundary of a specific range. The range defined in this way can include the end values or not include the end values, and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, the numerical range "a - b" represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0 - 7" means that all real numbers between "0 - 7" have been fully listed herein, and "0 - 7" is only an abbreviated representation of these numerical combinations. In addition, when it is stated that a certain parameter is an integer ≥3, it is equivalent to disclosing that the parameter is, for example, the integer 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0034] If there is no special description, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0035] If there is no special description, all technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0036] Unless otherwise specified, all steps of this application can be carried out sequentially or randomly, preferably sequentially. For example, the method includes steps (1) and (2), indicating that the method may include steps (1) and (2) carried out sequentially, or may also include steps (2) and (1) carried out sequentially. For example, when it is mentioned that the method may further include step (3), it means that step (3) can be added to the method in any order. For example, the method may include steps (1), (2), and (3), or may also include steps (1), (3), and (2), or may include steps (3), (1), and (2), etc.

[0037] Unless otherwise specified, the terms "comprising" and "including" mentioned in this application are open-ended and can also be closed-ended. For example, the "comprising" and "including" may mean that other components not listed may also be included or contained, or may only include or contain the listed components.

[0038] Unless otherwise specified, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); and / or both A and B are true (or exist).

[0039] This application provides a method for preparing an aqueous dispersion of a highly conductive polymer composite, which includes:

[0040] Step 1: Mix a dispersion of a composite containing a π-conjugated conductive polymer and a polyanion with a long-chain alkylbenzenesulfonic acid, and stir at room temperature for 1 min to 5 min to obtain a gel;

[0041] Step 2: Mix the gel with an aqueous organic solvent, and stir at room temperature for 1 min to 10 min to obtain a mixture;

[0042] Step 3: Filter the mixture, take the precipitate and mix it with a solvent, stir at room temperature for 1 min to 5 min, and filter again to obtain a highly conductive polymer composite;

[0043] Step 4: Mix the highly conductive polymer composite with pure water, and homogenize it under a high-pressure homogenizer to obtain an aqueous dispersion of the highly conductive polymer composite.

[0044] As used herein, the term "dispersion of a composite containing a π-conjugated conductive polymer and a polyanion" refers to a dispersion formed by dispersing a composite containing a π-conjugated conductive polymer and a polyanion in pure water, and the solid content of the dispersion is 0.5% to 2%.

[0045] As used herein, the term "π-conjugated conductive polymer" refers to an organic polymer molecule having a π-conjugated main chain, including but not limited to polypyrrole-based conductive polymers, polythiophene-based conductive polymers, or polyaniline-based conductive polymers.

[0046] As used herein, the term "polyanion" refers to a polymer having at least two anionic groups, and the anionic groups of the polyanion include but are not limited to sulfo groups or carboxyl groups.

[0047] As used herein, the term "long-chain alkylbenzenesulfonic acid" refers to a benzenesulfonic acid compound in which the alkyl chain of the main carbon chain has no less than 10 carbon atoms.

[0048] As used herein, the term "normal temperature" is 20 - 25 °C.

[0049] It has been found that, compared with the treatment of a complex dispersion containing a π-conjugated conductive polymer and a polyanion with a conventional solvent (dimethyl sulfoxide or ethylene glycol), in this application, a long-chain alkylbenzenesulfonic acid is first mixed with the complex dispersion containing a π-conjugated conductive polymer and a polyanion, and then an aqueous organic solvent is added, and a precipitate of a highly conductive polymer complex can be obtained by stirring at room temperature for several minutes. This process is short in process and time and does not require heating, greatly saving production costs. Moreover, the aqueous dispersion of the highly conductive polymer complex obtained by high-pressure homogenization of the highly conductive polymer complex has excellent stability, and the surface resistance of the film layer prepared therefrom is as low as 10 4 Ω / □, and its conductivity is significantly improved.

[0050] In addition, further mixing the precipitate with a solvent in step three is beneficial to removing the residues on the surface of the highly conductive polymer complex, minimizing the influence on the dispersion stability and conductivity of its aqueous dispersion.

[0051] In some embodiments, the stirring time in step one can be selected from 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min, or a value within the range formed by any two of the above values.

[0052] In some embodiments, the stirring time in step two can be selected from 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min, 5.5 min, 6 min, 6.5 min, 7 min, 7.5 min, 8 min, 8.5 min, 9 min, 9.5 min, 10 min, or a value within the range formed by any two of the above values.

[0053] In some embodiments, the stirring time in Step 3 can be selected from 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min, or a value within the range formed by any two of the above values.

[0054] In this application, a high-conductivity polymer composite aqueous dispersion can be obtained by subjecting a composite dispersion containing a π-conjugated conductive polymer and a polyanion to a short-time treatment, which greatly saves the production cost.

[0055] In some embodiments, the π-conjugated conductive polymer includes at least one of polypyrrole-based conductive polymers, polythiophene-based conductive polymers, and polyaniline-based conductive polymers, and is preferably a polythiophene-based conductive polymer.

[0056] In some embodiments, the polypyrrole-based conductive polymer includes at least one of polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), and poly(3-methyl-4-hexyloxypyrrole).

[0057] In some embodiments, the polythiophene-based conductive polymers include at least one of polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexoxythiophene), poly(3-heptoxythiophene), poly(3-octoxythiophene), poly(3-decoxythiophene), poly(3-dodecoxythiophene), poly(3-octadecoxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexoxythiophene), poly(3,4-diheptoxythiophene), poly(3,4-dioctoxythiophene), poly(3,4-didecoxythiophene), poly(3,4-didodecoxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxybutylthiophene).

[0058] In some embodiments, the polyaniline-based conductive polymers include at least one of polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), poly(3-anilinesulfonic acid).

[0059] In some embodiments, the polyanions include sulfopolymers and carboxyl polymers, preferably sulfopolymers.

[0060] In some embodiments, the sulfopolymers include at least one of polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, poly(4-sulfobutyl methacrylate), poly(sulfonatoethyl methacrylate), polymethacryloyloxybenzenesulfonic acid, poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprenesulfonic acid.

[0061] In some embodiments, the carboxyl polymers include at least one of polyvinylcarboxylic acid, polystyrenecarboxylic acid, polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropane carboxylic acid), polyisoprenecarboxylic acid.

[0062] In some embodiments, the long-chain alkylbenzenesulfonic acid includes at least one of C 10-16 alkylbenzenesulfonic acids. In some embodiments, the long-chain alkylbenzenesulfonic acid includes at least one of decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, and hexadecylbenzenesulfonic acid.

[0063] The long-chain alkylbenzenesulfonic acid with a main carbon chain of at least 10 carbon atoms can form a gel with the complex dispersion containing the π-conjugated conductive polymer and polyanion in a short time, improving the conductivity of the highly conductive polymer complex.

[0064] In some embodiments, the aqueous organic solvent includes at least one of alcohol solvents, ketone solvents, and ester solvents.

[0065] Alcohol solvents, ketone solvents, and ester solvents can all accelerate the generation of precipitation.

[0066] In some embodiments, the aqueous organic solvent includes at least one of alcohol solvents and ester solvents.

[0067] Alcohol solvents and ester solvents can both accelerate the generation of precipitation, and compared with ketone solvents such as methyl ethyl ketone, alcohol solvents and ester solvents are safer and non-toxic, which is beneficial to environmental protection.

[0068] In some embodiments, the solvent includes at least one of alcohol solvents and pure water.

[0069] In some embodiments, the alcohol solvents include at least one of methanol, ethanol, isopropanol, n-butanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, cyclohexanol, octanol, and allyl alcohol.

[0070] In some embodiments, the ketone solvents include at least one of methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl pentyl ketone, diethyl ketone, diisopropyl ketone, acetone, and diacetone alcohol.

[0071] In some embodiments, the ester solvents include at least one of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.

[0072] In some embodiments, the pressure of the high-pressure homogenizer is 100 bar to 800 bar, and the number of homogenization times of the high-pressure homogenizer is 3 to 8 times. In some embodiments, the pressure of the high-pressure homogenizer can be selected as 100 bar, 150 bar, 200 bar, 250 bar, 300 bar, 350 bar, 400 bar, 450 bar, 500 bar, 550 bar, 600 bar, 650 bar, 700 bar, 750 bar, 800 bar, or a value within the range formed by any two of the above values. The number of homogenization times of the high-pressure homogenizer can be selected as 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, or a value within the range formed by any two of the above values.

[0073] Controlling the pressure of the high-pressure homogenizer within a suitable range is beneficial to the formation of a stable aqueous dispersion of the highly conductive polymer composite.

[0074] In some embodiments, the mass ratio of the composite dispersion to the long-chain alkylbenzenesulfonic acid is (20 to 30):1. In some embodiments, the mass ratio of the composite dispersion to the long-chain alkylbenzenesulfonic acid is 20:1, 22:1, 24:1, 25:1, 26:1, 28:1, 30:1, or a ratio within the range formed by any two of the above ratios.

[0075] Controlling the mass ratio of the composite dispersion to the long-chain alkylbenzenesulfonic acid to be (20 to 30):1 can not only provide sufficient long-chain alkylbenzenesulfonic acid for mixing with the composite dispersion, but also avoid the excessive long-chain alkylbenzenesulfonic acid from affecting the dispersion stability of the composite containing the π-conjugated conductive polymer and the polyanion in subsequent pure water.

[0076] In some embodiments, the mass ratio of the composite dispersion to the water-based organic solvent is 1:(1.5 to 3). In some embodiments, the mass ratio of the composite dispersion to the water-based organic solvent is 1:1.5, 1:2, 1:2.5, 1:3, or a ratio within the range formed by any two of the above ratios.

[0077] Controlling the mass ratio of the composite dispersion to the water-based organic solvent to be 1:(1.5 to 3) can provide sufficient water-based organic solvent to accelerate the precipitation of the precipitate in the mixture, and at the same time can further improve the conductivity of the highly conductive polymer composite.

[0078] In some embodiments, the solid content of the aqueous dispersion of the highly conductive polymer composite is 0.5% to 1.5%. In some embodiments, the solid content of the aqueous dispersion of the highly conductive polymer composite can be selected as 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, or a value within the range formed by any two of the above values.

[0079] In some embodiments, the average particle size of the aqueous dispersion of the highly conductive polymer composite is 50 nm to 160 nm, and the PI value is 0.3 to 0.5. In some embodiments, the average particle size of the aqueous dispersion of the highly conductive polymer composite can be selected from 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, or a value within the range formed by any two of the above values, and the PI value can be selected from 0.3, 0.32, 0.34, 0.35, 0.36, 0.38, 0.4, 0.42, 0.44, 0.45, 0.46, 0.48, 0.5, or a value within the range formed by any two of the above values.

[0080] The average particle size of the aqueous dispersion of the highly conductive polymer composite prepared in this application is not higher than 160 nm, and the PI value is 0.3 to 0.5, which is beneficial to improving the stability of the aqueous dispersion of the highly conductive polymer composite and the electrical conductivity of the film formed therefrom.

[0081] In some embodiments, mixing the gel with an aqueous organic solvent and stirring at room temperature for 1 min to 10 min to obtain a mixture specifically includes:

[0082] Mixing the gel with a first aqueous organic solvent and stirring at room temperature for 1 min to 5 min, and then adding a second aqueous organic solvent and stirring at room temperature for 1 min to 5 min to obtain a mixture;

[0083] The first aqueous organic solvent includes at least one of a ketone solvent and an ester solvent, and the second aqueous organic solvent includes an alcohol solvent.

[0084] The precipitate formed by sequentially adding the first aqueous organic solvent and the second aqueous organic solvent and stirring for several minutes can be quickly filtered.

[0085] In some embodiments, mixing the gel with an aqueous organic solvent and stirring at room temperature for 1 min to 10 min to obtain a mixture specifically includes:

[0086] Mixing the gel with an alcohol solvent and stirring at room temperature for 1 min to 5 min to obtain a mixture.

[0087] Compared with sequentially adding the first aqueous organic solvent and the second aqueous organic solvent, the average particle size of the precipitate formed by adding the alcohol solvent in one step is relatively lower, which is beneficial to forming an aqueous dispersion with a smaller average particle size.

[0088] In some embodiments, the composite dispersion includes at least one of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) dispersion (PEDOT-PSS), polypyrrole-poly(styrenesulfonic acid) dispersion (PPy-PSS), polyaniline-poly(styrenesulfonic acid) dispersion (PANI-PSS), poly(3,4-ethylenedioxythiophene)-poly(vinylsulfonic acid) dispersion (PEDOT-PVS), and poly(3,4-ethylenedioxythiophene)-poly(acrylic acid) (PEDOT-PAS) dispersion.

[0089] This application provides a method for preparing a highly conductive polymer composite, including:

[0090] Mixing a composite dispersion containing a π-conjugated conductive polymer and a polyanion with a long-chain alkylbenzenesulfonic acid, and stirring at room temperature for 1 min to 5 min to obtain a gel;

[0091] Mixing the gel with an aqueous organic solvent, and stirring at room temperature for 1 min to 10 min to obtain a mixture;

[0092] Filtering the mixture, mixing the precipitate with a solvent, stirring at room temperature for 1 min to 5 min, and filtering again to obtain a highly conductive polymer composite.

[0093] This preparation method is simple, has a short production time, greatly saves production costs, and the highly conductive polymer composite has excellent conductive properties.

[0094] This application provides an antistatic liquid, including a resin, a solvent, an auxiliary agent, and an aqueous dispersion of a highly conductive polymer composite prepared by the preparation method in some embodiments;

[0095] Based on the total mass of the antistatic liquid, the mass content of the resin is 5% to 10%, the mass content of the solvent is 15% to 35%, the mass content of the auxiliary agent is 0.01% to 5%, and the mass content of the aqueous dispersion of the highly conductive polymer composite is 55% to 80%.

[0096] In some embodiments, based on the total mass of the antistatic liquid, the mass content of the resin can be optionally 5%, 6%, 7%, 8%, 9%, 10%, or a value within the range formed by any two of the above values; the mass content of the solvent can be optionally 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 28%, 30%, 32%, 34%, 35%, or a value within the range formed by any two of the above values; the mass content of the auxiliary agent can be optionally 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, or a value within the range formed by any two of the above values; the mass content of the aqueous dispersion of the highly conductive polymer composite can be optionally 55%, 56%, 58%, 60%, 62%, 64%, 65%, 66%, 68%, 70%, 72%, 74%, 75%, 76%, 78%, 80%, or a value within the range formed by any two of the above values.

[0097] As used herein, the term "resin" refers to some water-soluble resins, including but not limited to acrylate resins.

[0098] In some embodiments, the solvent includes pure water.

[0099] In some embodiments, the auxiliary agent includes at least one of a surfactant and an antifoaming agent.

[0100] This application presents the application of the aqueous dispersion of the highly conductive polymer composite prepared by the preparation method in some embodiments in flexible electronic devices and sensors.

[0101] Examples

[0102] The following examples are for better further understanding of the present invention, and are not limited to the best embodiments, and do not constitute limitations on the content and protection scope of the present invention. For those examples where specific experimental steps or conditions are not indicated, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For reagents or instruments whose manufacturers are not indicated, they are all conventional reagent products that can be obtained through commercial purchase.

[0103] I. Preparation method

[0104] Example 1

[0105] Preparation of the aqueous dispersion of the highly conductive polymer composite:

[0106] Step 1: Place the PEDOT-PSS composite dispersion (purchased from Shanghai Ouyi Organic Optoelectronic Materials Co., Ltd., with a solid content of 1.3%, the same hereinafter) and dodecylbenzenesulfonic acid in a beaker according to a mass ratio of 25:1, stir at 600 rmp for 3 min to obtain a gel;

[0107] Step 2: Add the above gel to isopropanol (the mass ratio of the PEDOT-PSS composite dispersion to isopropanol is 1:2), stir at 600 rmp for 2 min to obtain a mixture;

[0108] Step 3: Filter the above mixture, take the precipitate and mix it with ethanol (the mass ratio of the PEDOT-PSS composite dispersion to ethanol is 1:2), stir at 600 rmp for 2 min, filter again, then mix the precipitate with pure water (the mass ratio of the PEDOT-PSS composite dispersion to pure water is 1:2), stir at 600 rmp for 2 min, and filter again to obtain a highly conductive polymer composite;

[0109] Step 4: Mix the above highly conductive polymer composite and pure water and homogenize it under a high-pressure homogenizer at a pressure of 400 bar for 3 times to obtain a highly conductive PEDOT-PSS aqueous dispersion with a solid content of 0.9%.

[0110] Preparation of the antistatic liquid: Mix the above highly conductive PEDOT-PSS dispersion, polyester resin TH-100, pure water, fluorocarbon surfactant FC-4430, and silicone defoamer DF-880 according to a mass ratio of 6:0.45:1.8:0.01:0.001 to prepare the antistatic liquid.

[0111] Examples 2 - 3

[0112] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 2 - 3 are similar to those in Example 1, except that: the dodecylbenzenesulfonic acid, the raw material for preparing the aqueous dispersion of the highly conductive polymer composite in Example 1, is adjusted to decylbenzenesulfonic acid and tridecylbenzenesulfonic acid respectively, as shown in Tables 1 and 2 specifically.

[0113] Examples 4 - 5

[0114] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 4 - 5 are similar to those in Example 1, except that: the isopropanol, the raw material for preparing the aqueous dispersion of the highly conductive polymer composite in Example 1, is adjusted to ethyl acetate and methanol respectively, as shown in Tables 1 and 2 specifically.

[0115] Example 6

[0116] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Example 6 are similar to those in Example 1, except that: the isopropanol, the raw material for preparing the aqueous dispersion of the highly conductive polymer composite in Example 1, is adjusted to methyl isobutyl ketone + isopropanol, and the specific steps are as follows:

[0117] Step 1: Place the PEDOT-PSS composite dispersion and dodecylbenzenesulfonic acid in a beaker at a mass ratio of 25:1, stir at 600 rmp for 3 min to obtain a gel.

[0118] Step 2: Add the above gel to methyl isobutyl ketone (the mass ratio of the PEDOT-PSS composite dispersion to methyl isobutyl ketone is 1:1), stir at 600 rmp for 2 min, then add isopropanol (the mass ratio of the PEDOT-PSS composite dispersion to isopropanol is 1:1), stir at 600 rmp for 2 min to obtain a mixture.

[0119] Step 3: Filter the above mixture, mix the precipitate with ethanol (the mass ratio of the PEDOT-PSS composite dispersion to ethanol is 1:2), stir at 600 rmp for 2 min, filter again, then mix the precipitate with pure water (the mass ratio of the PEDOT-PSS composite dispersion to pure water is 1:2), stir at 600 rmp for 2 min, and filter again to obtain a highly conductive polymer composite.

[0120] Step 4: Mix the above highly conductive polymer composite and pure water and homogenize it under a high-pressure homogenizer at a pressure of 400 bar for 3 times to obtain a highly conductive PEDOT-PSS dispersion with a solid content of 0.9%.

[0121] Examples 7 - 8

[0122] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 7 - 8 are similar to those in Example 1, except that the mass ratios of the composite dispersion to long-chain alkylbenzenesulfonic acid in the preparation of the aqueous dispersion of the highly conductive polymer composite in Example 1 are adjusted to 20:1 and 30:1 respectively.

[0123] Examples 9 - 10

[0124] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 9 - 10 are similar to those in Example 1, except that the mass ratios of the composite dispersion to the water-based organic solvent in the preparation of the aqueous dispersion of the highly conductive polymer composite in Example 1 are adjusted to 1:1.5 and 1:3 respectively.

[0125] Examples 11 - 12

[0126] The preparation of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Examples 11 to 12 is similar to that of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Example 1, except that the stirring times in Step 1 of the preparation of the aqueous dispersions of the highly conductive polymer composites in Example 1 are adjusted to 1 min and 5 min respectively.

[0127] Examples 13 to 14

[0128] The preparation of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Examples 13 to 14 is similar to that of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Example 1, except that the stirring times in Step 2 of the preparation of the aqueous dispersions of the highly conductive polymer composites in Example 1 are adjusted to 1 min and 5 min respectively.

[0129] Examples 15 to 16

[0130] The preparation of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Examples 15 to 16 is similar to that of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Example 1, except that the stirring times in Step 3 of the preparation of the aqueous dispersions of the highly conductive polymer composites in Example 1 are adjusted to 2 min and 5 min respectively (the stirring time is 2 min after mixing with ethanol and 3 min after mixing with pure water).

[0131] Examples 17 to 18

[0132] The preparation of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Examples 17 to 18 is similar to that of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Example 1, except that the pressures of the high-pressure homogenizer in the preparation of the aqueous dispersions of the highly conductive polymer composites in Example 1 are adjusted to 100 bar and 800 bar respectively.

[0133] Examples 19 to 20

[0134] The preparation of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Examples 19 to 20 is similar to that of the aqueous dispersions of the highly conductive polymer composites and the antistatic liquids in Example 1, except that the solid contents in the preparation of the aqueous dispersions of the highly conductive polymer composites in Example 1 are adjusted to 0.5% and 1.5% respectively.

[0135] Examples 21 to 22

[0136] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 21 to 22 are similar to those in Example 1, except that the mass contents of the aqueous dispersion of the highly conductive polymer composite in the antistatic liquid in Example 1 are adjusted to 55% and 80% respectively (the contents of other substances are reduced proportionally to achieve the adjustment of the mass content of the aqueous dispersion of the highly conductive polymer composite).

[0137] Examples 23 to 25

[0138] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 23 to 25 are similar to those in Example 1, except that the raw material PEDOT-PSS composite dispersion liquid for preparing the aqueous dispersion of the highly conductive polymer composite in Example 1 is adjusted to PPy-PSS composite dispersion liquid (purchased from Shanghai Macklin Biochemical Co., Ltd., solid content 1.3%), PANI-PSS composite dispersion liquid (purchased from Shanghai Macklin Biochemical Co., Ltd., solid content 1.5%), and PEDOT-PVS composite dispersion liquid (purchased from Shanghai Ouyi Organic Optoelectronic Materials Co., Ltd., solid content 1.3%) respectively. See Tables 1 and 2 for details.

[0139] Comparative Example

[0140] Comparative Example 1

[0141] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Comparative Example 1 are similar to those in Example 1, except that dodecylbenzenesulfonic acid, the raw material for preparing the aqueous dispersion of the highly conductive polymer composite in Example 1, is not introduced. The specific steps are as follows:

[0142] Put the PEDOT-PSS composite dispersion liquid and isopropanol in a beaker at a mass ratio of 1:2, stir at 600 rmp for 1 h, and no gel is obtained; filtering the mixture fails to obtain a precipitate, and the experiment is aborted.

[0143] Comparative Example 2

[0144] The preparation of the aqueous dispersion of the highly conductive polymer composite and the antistatic liquid in Comparative Example 2 are similar to those in Example 1, except that dodecylbenzenesulfonic acid, the raw material for preparing the aqueous dispersion of the highly conductive polymer composite in Example 1, is adjusted to p-toluenesulfonic acid. The specific steps are as follows:

[0145] Put the PEDOT-PSS composite dispersion liquid and p-toluenesulfonic acid in a beaker at a mass ratio of 25:1, stir at 600 rmp for 1 h, and no gel is obtained;

[0146] The above mixture was added to isopropanol (the mass ratio of the PEDOT-PSS composite dispersion to isopropanol was 1:2), stirred at 600 rmp for 1 h, and no precipitate was obtained after filtration, so the experiment was terminated.

[0147] Comparative Example 3

[0148] The preparation of the high-conductivity polymer composite aqueous dispersion and the antistatic liquid in Comparative Example 1 was similar to that in Example 1, except that the PEDOT-PSS dispersion was directly dried without surfactant precipitation treatment. The specific steps were as follows:

[0149] The PEDOT-PSS composite dispersion was freeze-dried, then redispersed in water, and subjected to high-pressure homogenization to obtain a new dispersion.

[0150] Comparative Example 4

[0151] The preparation of the high-conductivity polymer composite aqueous dispersion and the antistatic liquid in Comparative Example 4 was similar to that in Example 1, except that dodecylbenzenesulfonic acid, the raw material for preparing the high-conductivity polymer composite aqueous dispersion in Example 1, was not introduced. The specific steps were as follows:

[0152] The PEDOT-PSS composite dispersion, methanol, and methyl ethyl ketone were placed in a beaker according to a mass ratio of 100:12.5:200, stirred at 600 rmp at 70 °C for 4 h, and after mixing, the mixture was allowed to stand and then filtered to obtain the precipitate;

[0153] The above precipitate was mixed with ethanol (the mass ratio of the PEDOT-PSS composite dispersion to ethanol was 1:2), stirred at 600 rmp for 5 min, filtered again, and then the precipitate was mixed with pure water (the mass ratio of the PEDOT-PSS composite dispersion to pure water was 1:2), stirred at 600 rmp for 5 min, and filtered again to obtain the conductive polymer composite;

[0154] The above high-conductivity polymer composite and pure water were mixed and homogenized under a high-pressure homogenizer at a pressure of 400 bar for 3 times to obtain a conductive PEDOT-PSS dispersion with a solid content of 0.9%.

[0155] Comparative Example 5

[0156] The preparation of the high-conductivity polymer composite aqueous dispersion and the antistatic liquid in Comparative Example 5 was similar to that in Example 1, except that dodecylbenzenesulfonic acid, the raw material for preparing the high-conductivity polymer composite aqueous dispersion in Example 1, was not introduced. The specific steps were as follows:

[0157] The PEDOT-PSS composite dispersion and methyl ethyl ketone were placed in a beaker at a mass ratio of 1:2, stirred at 600 rmp for 6 h at 70 °C, and no precipitate was obtained.

[0158] The above system was homogenized in a high-pressure homogenizer at a pressure of 400 bar for 3 times to obtain a conductive PEDOT-PSS dispersion with a solid content of 0.43%.

[0159] Table 1 Preparation parameters of the high-conductive polymer composite aqueous dispersion

[0160]

[0161]

[0162] Table 2 Preparation parameters of the high-conductive polymer composite aqueous dispersion

[0163]

[0164]

[0165] II. Test methods

[0166] 1) Test of the average particle size and PI value of the high-conductive polymer composite aqueous dispersion

[0167] The test of the average particle size of the modified nanoparticles was carried out with reference to the standard of GB / T 19077.1-2003. The high-conductive polymer composite aqueous dispersion was tested using a Horiba SZ-100V2 nanoparticle size analyzer to obtain the particle size distribution curve of the high-conductive polymer composite aqueous dispersion. The average particle size and PI value of the high-conductive polymer composite aqueous dispersion can be directly obtained from the particle size distribution curve.

[0168] 2) Test of the surface resistance of the film layer formed from the high-conductive polymer composite aqueous dispersion

[0169] Film formation of the high-conductive polymer composite aqueous dispersion: The high-conductive polymer composite aqueous dispersion to be tested was mixed with a fluorocarbon surfactant at a mass ratio of 10,000:1, and coated on a corona-treated PET substrate using a #6 wire bar, and dried in an oven at 120 °C for 1 minute to obtain its film layer.

[0170] The surface resistance property of the film layer sample prepared by coating the above high-conductive polymer composite aqueous dispersion was tested using a surface resistance device, and the model of the test device was SIMCO ST-4 surface resistance meter.

[0171] 3) Test of the surface resistance of the film formed from the antistatic liquid

[0172] Anti-static liquid film formation: Using an isopropanol: pure water = 1:1 solution as a diluent, the anti-static liquid to be tested is diluted 1:10, and then coated on a corona-treated PET substrate using a #6 wire bar, and dried in an oven at 120 degrees for 1 minute to obtain its film layer.

[0173] Use a surface resistance tester to measure the surface resistance properties of the film layer samples prepared by coating the above anti-static liquid. The model of the testing equipment is SIMCO ST-4 surface resistance meter.

[0174] Table 3 Performance parameters of each example and comparative example

[0175]

[0176] III. Analysis of test results of each example and comparative example

[0177] It can be seen from Examples 1 to 24 and Comparative Examples 1 to 5 that the preparation method of the present application takes a short time, can achieve the preparation of high-conductive polymer composites without heating, and the average particle size of its aqueous dispersion is lower than 160 nm and the PI value is not higher than 0.5, which is beneficial to improving the dispersion stability of the aqueous dispersion. More importantly, the high-conductive polymer composite aqueous dispersion and its anti-static liquid coating film both have a low surface resistance, that is, they have excellent conductive properties.

[0178] It can be seen from Example 1 and Comparative Example 3 that compared with the PEDOT-PSS composite dispersion without treatment with dodecylbenzenesulfonic acid, the high-conductive PEDOT-PSS aqueous dispersion treated with dodecylbenzenesulfonic acid has a lower average particle size and a smaller PI value, and also has a lower intrinsic coating film surface resistance and a formulated coating film surface resistance. This is because the addition of dodecylbenzenesulfonic acid can effectively strip the excess PSS component in the PEDOT-PSS composite, reduce the proportion of non-conductive PSS components in the coating film, and thus greatly improve the intrinsic and formulated coating film surface resistance.

[0179] It can be seen from Examples 1 to 3 and Comparative Examples 1 to 2 that the introduction of long-chain alkylbenzenesulfonic acid in the preparation process of high-conductive PEDOT-PSS aqueous dispersion is very important. Without adding long-chain alkylbenzenesulfonic acid or with too short an alkyl chain, the formation of gel or precipitation cannot be achieved, and thus the improvement of its conductive performance cannot be achieved.

[0180] It can be seen from Examples 1 to 3 and Comparative Examples 4 to 5 that compared with the treatment of PEDOT-PSS complex with alcohol solvents / ketone solvents, the treatment of PEDOT-PSS complex with long-chain alkylbenzenesulfonic acid combined with alcohol solvents / ketone solvents / ester solvents can not only reduce the treatment time and heating energy, but also is beneficial to further improving its conductive performance.

[0181] As can be seen from Examples 1, 4 to 6, alcohol solvents, ester solvents or ketone solvents can all accelerate the formation of precipitation, and can all achieve high dispersion stability of the highly conductive PEDOT-PSS aqueous dispersion and its high conductivity. As can be seen from Examples 1 and 6, after replacing isopropyl alcohol with methyl isobutyl ketone + isopropyl alcohol, the precipitation formation rate will be faster and the precipitation particles will be larger, which is beneficial to reducing the filtration time and further reducing the production time.

[0182] As can be seen from Examples 7 to 8 and Examples 11 to 12, the interaction between dodecylbenzenesulfonic acid and the PEDOT-PSS complex will be affected by the addition amount of dodecylbenzenesulfonic acid and the stirring time. Too little surfactant addition amount or too short stirring time will weaken the formation effect of gel and precipitation, and thus bring about a weaker improvement in conductivity.

[0183] As can be seen from Examples 9 to 10 and Examples 13 to 16, the addition amount of water-soluble organic solvents and the stirring time, as well as the stirring time of the cleaning step, have no effect on the formation quality of PEDOT-PSS precipitation.

[0184] As can be seen from Examples 17 to 18, high-pressure homogenization of PEDOT-PSS precipitation is relatively easy, and a highly conductive PEDOT-PSS aqueous dispersion can be obtained using a relatively low homogenization pressure. However, when the homogenization pressure is too high, the conductivity of the aqueous dispersion, especially the film conductivity of its antistatic liquid, will decrease.

[0185] As can be seen from Examples 19 to 20, when the solid content of the dispersion is relatively high, the viscosity of the PEDOT-PSS aqueous dispersion after homogenization will increase significantly. Compared with the aqueous dispersion with a low solid content, when the liquid addition amount is the same, the PEDOT-PSS aqueous dispersion with a high solid content will have a larger PEDOT addition amount in the antistatic liquid, so an antistatic liquid film with a lower surface resistance can be achieved.

[0186] As can be seen from Examples 21 to 22, when the addition amount of the highly conductive PEDOT-PSS aqueous dispersion in the antistatic liquid is increased or decreased, the surface resistance of the antistatic liquid film will correspondingly decrease or increase.

[0187] As can be seen from Examples 1 and Examples 23 to 25, the preparation method of the present application is widely applicable to different types of composite dispersion liquid systems containing π-conjugated conductive polymers and polyanions, and can make their aqueous dispersions have a lower average particle size and PI value, as well as the high conductivity of the film.

[0188] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the various embodiments of the present application, and they should all be covered by the scope of the claims and the specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in each embodiment can be combined in any way. The present application is not limited to the specific embodiments disclosed in the text, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A method for preparing an aqueous dispersion of a highly conductive polymer composite, characterized in that: include: Step 1: mixing a composite dispersion containing a π-conjugated conductive polymer and a polyanion with a long-chain alkylbenzene sulfonic acid, and stirring at room temperature for 1 to 5 minutes to obtain a gel; Step 2: mixing the gel with an aqueous organic solvent, stirring at room temperature for 1 min to 10 min to obtain a mixture; Step 3: filtering the mixture, taking the precipitate and mixing it with the solvent, stirring it at room temperature for 1 min to 5 min, and filtering it again to obtain a highly conductive polymer composite; Step 4: Mix the highly conductive polymer composite and pure water, and homogenize them in a high-pressure homogenizer to obtain the highly conductive polymer composite aqueous dispersion.

2. The preparation method according to claim 1, characterized in that: The π-conjugated conductive polymer includes at least one of a polypyrrole conductive polymer, a polythiophene conductive polymer, and a polyaniline conductive polymer, and optionally includes a polythiophene conductive polymer; and / or The polyanion comprises a sulfonic polymer and a carboxylic polymer, optionally comprising a sulfonic polymer; and / or The long chain alkylbenzene sulfonic acid includes C 10-16 At least one of alkylbenzene sulfonic acids; and / or The aqueous organic solvent comprises at least one of an alcohol solvent, a ketone solvent, and an ester solvent; and / or The solvent comprises at least one of an alcohol solvent and pure water; and / or The pressure of the high-pressure homogenizer is 100 bar to 800 bar, and the homogenization times of the high-pressure homogenizer is 3 to 8 times.

3. The preparation method according to claim 1, characterized in that: The solid content of the composite dispersion is 0.5% to 2%; and / or The mass ratio of the composite dispersion to the long-chain alkylbenzene sulfonic acid is (20-30):1; and / or The mass ratio of the composite dispersion to the aqueous organic solvent is 1:(1.5-3); and / or The solid content of the highly conductive polymer composite aqueous dispersion is 0.5% to 1.5%, and can be 0.5% to 1.2%; and / or The average particle size of the highly conductive polymer composite aqueous dispersion is 50 nm to 160 nm, and may be 50 nm to 100 nm, and the PI value is 0.3 to 0.5, and may be 0.35 to 0.

45.

4. The preparation method according to claim 1, characterized in that: The gel is mixed with an aqueous organic solvent and stirred at room temperature for 1 to 10 minutes to obtain a mixture, which specifically includes: The gel is mixed with a first aqueous organic solvent, and stirred at room temperature for 1 to 5 minutes, and then a second aqueous organic solvent is added, and stirred at room temperature for 1 to 5 minutes to obtain the mixture; The first aqueous organic solvent includes at least one of a ketone solvent and an ester solvent, and the second aqueous organic solvent includes an alcohol solvent.

5. The preparation method according to claim 1, characterized in that: The gel is mixed with an aqueous organic solvent and stirred at room temperature for 1 to 10 minutes to obtain a mixture, which specifically includes: The gel is mixed with an alcohol solvent and stirred at room temperature for 1 min to 5 min to obtain the mixture.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The polythiophene conductive polymer includes at least one of poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-bromothiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), and poly(3-methyl-4-carboxyethylthiophene); and / or The sulfonic polymer includes at least one of polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, poly(4-sulfobutyl methacrylate), polymethacryloxybenzene sulfonic acid, polysulfoethyl methacrylate, poly(2-acrylamido-2-methylpropane sulfonic acid), and polyisoprene sulfonic acid; and / or The long-chain alkylbenzene sulfonic acid comprises at least one of decylbenzene sulfonic acid, dodecylbenzene sulfonic acid, tetradecylbenzene sulfonic acid and hexadecylbenzene sulfonic acid; and / or The alcohol solvent includes at least one of methanol, ethanol, isopropanol, n-butanol, n-butanol, isobutanol, sec-butanol and tert-butanol, n-pentanol, isopentanol, cyclohexanol, octanol and allyl alcohol; the ketone solvent includes at least one of methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl amyl ketone, diethyl ketone, diisopropyl ketone and diacetone alcohol; the ester solvent includes at least one of methyl acetate, ethyl acetate, propyl acetate and butyl acetate.

7. The preparation method according to any one of claims 1 to 5, characterized in that The composite dispersion includes at least one of poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) dispersion, polypyrrole-poly(styrene sulfonic acid) dispersion, polyaniline-poly(styrene sulfonic acid) dispersion, poly(3,4-ethylenedioxythiophene)-poly(ethylene sulfonic acid) dispersion, and poly(3,4-ethylenedioxythiophene)-polyacrylic acid dispersion.

8. A method for preparing a highly conductive polymer composite, characterized in that: include: The composite dispersion containing the π-conjugated conductive polymer and the polyanion is mixed with a long-chain alkylbenzene sulfonic acid, and stirred at room temperature for 1 to 5 minutes to obtain a gel; The gel is mixed with an aqueous organic solvent and stirred at room temperature for 1 to 10 minutes to obtain a mixture; The mixture is filtered, and the precipitate is mixed with a solvent, stirred at room temperature for 1 min to 5 min, and filtered again to obtain the highly conductive polymer composite.

9. An antistatic liquid, characterized in that: A highly conductive polymer composite aqueous dispersion comprising a resin, a solvent, an additive, and the preparation method according to any one of claims 1 to 7; Based on the total mass of the antistatic liquid, the mass content of the resin is 5% to 10%, the mass content of the solvent is 15% to 35%, the mass content of the auxiliary agent is 0.01% to 5%, and the mass content of the highly conductive polymer composite aqueous dispersion is 55% to 80%.

10. Use of an aqueous dispersion of a highly conductive polymer composite prepared by the preparation method according to any one of claims 1 to 7 in flexible electronic devices and sensors.

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