Preparation method and application of high-conductivity polymer compound and organic solvent dispersion liquid thereof

Abstract

The invention discloses a high-conductivity polymer compound and a preparation method and application of organic solvent dispersion liquid of the high-conductivity polymer compound. According to the preparation method, long-chain alkyl benzene sulfonic acid is introduced into a compound dispersion liquid containing a pi-conjugated conductive polymer and polyanions to weaken coulomb force between the pi-conjugated conductive polymer and a polyanion chain, and then a water-based organic solvent is used for rapidly intensifying precipitation of a high-conductivity polymer compound precipitate. Meanwhile, an organic modifier is introduced for surface modification, finally, the high-conductivity polymer compound organic solvent dispersion liquid with excellent stability is prepared by re-homogenizing the precipitated modified high-conductivity polymer compound under the action of a high-pressure homogenizer, and the preparation method is simple in process, short in time consumption, free of heating and low in production cost; and the construction of green production economy is facilitated.

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 organic solvent dispersion liquid. Background Art

[0002] π-conjugated conductive polymers have excellent properties such as flexibility, low cost, and solution processability. They can be easily coated on substrates such as plastics and glass by solution methods such as wire bar coating, gravure coating, spraying, printing, etc., and are widely used in applications such as antistatic release films, antistatic protective films, and touch panels as antistatic coatings and conductive electrodes.

[0003] Generally, the dispersion liquid of π-conjugated conductive polymers such as PEDOT-PSS is an aqueous solution, so most of the formulation components paired with it also need to be water-soluble components. Aqueous formulation coating liquids also have advantages such as environmental protection and non-flammability and explosiveness. However, the boiling point of water is fixed at 100 °C and cannot be adjusted. Compared with coating liquids of organic solvent types, especially those based on low-boiling organic solvents such as ethanol, isopropanol, and ethyl acetate, the drying speed of aqueous coating liquids is slower, and the coating film requires a longer drying time, which will limit the actual coating speed and production efficiency. At the same time, compared with organic solvents, the surface energy of water is also relatively high, which is not conducive to the wetting of the coating on the substrate surface. Various additives such as surfactants need to be paired in the formulation to enhance the leveling and wetting effects of the aqueous coating. In addition, the sources of raw materials based on organic solvents, such as resin materials, are also richer, which is more conducive to the formulation and preparation of coatings.

[0004] Therefore, developing a π-conjugated conductive polymer dispersion liquid based on organic solvents can be easily paired with other formulation components of organic solvent types, which is very beneficial for obtaining an organic solvent coating liquid with a fast drying speed and high wettability and a coating film with high transparency, low haze, and high uniformity. It has very important practical significance for the development of antistatic coatings of organic solvent types. Summary of the Invention

[0005] Therefore, the technical problem to be solved by this application is to overcome the above defects in the prior art. Its purpose is to provide a method for preparing an organic solvent dispersion of a highly conductive polymer composite. By introducing long-chain alkylbenzenesulfonic acid into the composite dispersion containing π-conjugated conductive polymer and polyanion, the Coulomb force between the π-conjugated conductive polymer and the polyanion chain is weakened. Subsequently, the precipitation of the highly conductive polymer composite is rapidly accelerated by using an aqueous organic solvent, and at the same time, an organic modifier is introduced for surface modification. Finally, the precipitated modified highly conductive polymer composite is homogenized again under the action of a high-pressure homogenizer to prepare an organic solvent dispersion of a highly conductive polymer composite with excellent stability. Moreover, the preparation method has simple process, short time consumption, no need for heating, low production cost, and is conducive to the construction of a green production economy.

[0006] In the first aspect of this application, a method for preparing an organic solvent dispersion of a highly conductive polymer composite is provided, including:

[0007] Step 1: Mix the composite dispersion containing π-conjugated conductive polymer and polyanion with long-chain alkylbenzenesulfonic acid, and stir at room temperature for 3 min to 10 min to obtain a gel;

[0008] Step 2: Mix the gel with an aqueous organic solvent, and stir at room temperature for 1 min to 10 min; then add an organic modifier and stir at room temperature for 10 min to 60 min to obtain a mixture;

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

[0010] Step 4: Mix the highly conductive polymer composite with a second organic solvent and homogenize it under a high-pressure homogenizer to obtain the organic solvent dispersion of the highly conductive polymer composite.

[0011] Research has found that in this application, first, the composite dispersion containing π-conjugated conductive polymer and polyanion is mixed with long-chain alkylbenzenesulfonic acid, then an aqueous organic solvent is added, stirred at room temperature for several minutes, and then an organic modifier is introduced and stirred at room temperature for dozens of minutes, so as to obtain a surface-modified highly conductive polymer composite precipitate, which greatly reduces the processing time and energy consumption. Moreover, the organic solvent dispersion of the highly conductive polymer composite obtained by homogenizing the modified highly conductive polymer composite and the second organic solvent under a high-pressure homogenizer has excellent stability. The surface resistance of the film layer prepared from the organic solvent 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 C 10-16 at least one of alkylbenzenesulfonic acids.

[0015] In any embodiment, the aqueous organic solvent includes at least one of alcohol solvents, ketone solvents, and ester solvents.

[0016] In any embodiment, the first organic solvent includes alcohol solvents.

[0017] In any embodiment, the second organic solvent includes alcohol solvents.

[0018] In any embodiment, the organic modifier includes at least one of organic amine compounds and epoxy compounds.

[0019] In any embodiment, the organic amine compounds include at least one of octylamine, aniline, toluidine, benzylamine, ethanolamine, diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine, triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.

[0020] In any embodiment, the epoxy compounds include at least one of ethylene oxide, propylene oxide, 2,3-epoxybutane, epoxybutane, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, 1,2-epoxyeicosane, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, p-tert-butylphenyl glycidyl ether, o-tolyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, cardanol glycidyl ether, 1,2-epoxy-4-vinylcyclohexane, and diallyl monoglycidyl isocyanurate.

[0021] In any embodiment, the solid content of the high-conductive polymer composite organic solvent dispersion is 0.5% to 1.5%.

[0022] In any embodiment, the average particle size of the organic solvent dispersion of the highly conductive polymer composite is 50 nm to 130 nm, optionally 70 nm to 120 nm, and the PI is 0.2 to 0.45, optionally 0.25 to 0.4.

[0023] In any embodiment, mixing the gel with an aqueous organic solvent and stirring at room temperature for 1 min to 10 min; then adding an organic modifier and stirring at room temperature for 10 min to 60 min, the obtained mixture specifically includes:

[0024] Mixing the gel with a first aqueous organic solvent and stirring at room temperature for 1 min to 5 min, then adding a second aqueous organic solvent and stirring at room temperature for 1 min to 5 min; then adding an organic modifier and stirring at room temperature for 10 min to 60 min to obtain the mixture;

[0025] Wherein, 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.

[0026] In any embodiment, mixing the gel with an aqueous organic solvent and stirring at room temperature for 1 min to 10 min; then adding an organic modifier and stirring at room temperature for 10 min to 60 min, the obtained mixture specifically includes:

[0027] Mixing the gel with an alcohol solvent and stirring at room temperature for 1 min to 5 min; then adding an organic modifier and stirring at room temperature for 10 min to 60 min to obtain the mixture.

[0028] 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.

[0029] In a second aspect of the present application, a method for preparing an organic solvent dispersion of a highly conductive polymer composite is provided, including:

[0030] Step 1: 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 3 min to 10 min to obtain a gel;

[0031] Step 2: Mixing the gel with an aqueous organic solvent and stirring at room temperature for 1 min to 10 min to obtain a mixture;

[0032] Step 3: Filter the mixture, mix the precipitate with a first organic solvent, stir at room temperature for 1 min to 5 min, and filter again to obtain a highly conductive polymer composite;

[0033] Step 4: Mix the highly conductive polymer composite, an organic modifier, and a second organic solvent, and perform homogenization under a high-pressure homogenizer to obtain the organic solvent dispersion of the highly conductive polymer composite.

[0034] In a third aspect of the present application, a method for preparing a highly conductive polymer composite is provided, including:

[0035] Mix a composite dispersion containing a π-conjugated conductive polymer and a polyanion with a long-chain alkylbenzenesulfonic acid, and stir at room temperature for 3 min to 10 min to obtain a gel;

[0036] Mix the gel with an aqueous organic solvent, stir at room temperature for 1 min to 10 min, then add an organic modifier, and stir at room temperature for 10 min to 60 min to obtain the mixture;

[0037] Filter the mixture, mix the precipitate with an organic solvent, stir at room temperature for 1 min to 5 min, and filter again to obtain the highly conductive polymer composite.

[0038] In a fourth aspect of the present application, an antistatic liquid is provided, including a resin, a solvent, and an organic solvent 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 2% to 10%, the mass content of the solvent is 15% to 35%, and the mass content of the organic solvent dispersion of the highly conductive polymer composite is 55% to 80%.

[0039] In a fourth aspect of the present application, an application of the organic solvent 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

[0040] Hereinafter, embodiments of the preparation method and application of the highly conductive polymer composite and its organic solvent dispersion of the present application will be specifically 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 prevent 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 identical 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.

[0041] 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 or exclude 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 integers 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0042] If there is no special instruction, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0043] If there is no special instruction, all technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0044] If there is no special instruction, all steps of the present application can be carried out in sequence or randomly, and preferably in sequence. For example, the method includes steps (1) and (2), which means that the method can include steps (1) and (2) carried out in sequence, or can also include steps (2) and (1) carried out in sequence. 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 can include steps (1), (2) and (3), or can also include steps (1), (3) and (2), or can also include steps (3), (1) and (2), etc.

[0045] Unless otherwise specified, the terms "comprising" and "including" mentioned in this application are open-ended and can also be closed-ended. For example, the terms "comprising" and "including" can mean that other components not listed may also be included or comprised, or that only the listed components are included or comprised.

[0046] 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 present) and B is false (or absent); A is false (or absent) while B is true (or present); or both A and B are true (or present).

[0047] This application provides a method for preparing an organic solvent dispersion of a highly conductive polymer composite, comprising:

[0048] Step 1: 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 3 min to 10 min to obtain a gel;

[0049] Step 2: Mix the gel with an aqueous organic solvent, and stir at room temperature for 1 min to 10 min; then add an organic modifier and stir at room temperature for 10 min to 60 min to obtain a mixture;

[0050] Step 3: Filter the mixture, take the precipitate and mix it with a first organic solvent, stir at room temperature for 1 min to 5 min, and filter again to obtain a highly conductive polymer composite;

[0051] Step 4: Mix the highly conductive polymer composite with a second organic solvent, and perform homogenization in a high-pressure homogenizer to obtain an organic solvent dispersion of the highly conductive polymer composite.

[0052] In this text, the term "composite dispersion 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%.

[0053] In this text, 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.

[0054] In this text, 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.

[0055] In this text, the term "long-chain alkylbenzenesulfonic acid" refers to benzenesulfonic acid compounds with an alkyl chain of no less than 10 carbons.

[0056] In this text, the term "room temperature" is 20 - 25 °C.

[0057] Currently, dispersions containing π-conjugated conductive polymers and polyanions all have the disadvantage of low conductivity. Using modifiers to modify them to prepare an organic solvent dispersion system still has conductivity problems. Conventional improvement measures, such as treating the π-conjugated conductive polymer or polyanion with dimethyl sulfoxide or ethylene glycol solvents, or doping and modifying the π-conjugated conductive polymer or polyanion, still have problems such as excessively high production costs for solvent treatment, the impact of doping modification on its stability, and limited improvement in conductivity. The research of this application finds that by first mixing long-chain alkylbenzenesulfonic acid with a complex dispersion containing π-conjugated conductive polymers and polyanions, then adding a water-based organic solvent, and introducing an organic modifier at the same time, a precipitate of a surface-modified highly conductive polymer complex can be obtained by stirring at room temperature for dozens of minutes. This process is simple, takes a short time, and does not require heating up, greatly saving production costs. Moreover, the organic solvent dispersion of the highly conductive polymer complex obtained by high-pressure homogenization of the highly conductive polymer complex has excellent stability and light transmittance, and the surface resistance of the film layer prepared therefrom is as low as 10 4 Ω / □, and its conductivity is significantly improved.

[0058] In addition, further mixing and stirring the precipitate with a second organic solvent in step three and then filtering is beneficial to removing the residues on the surface of the highly conductive polymer complex, minimizing the impact on the dispersion stability and conductivity of its organic solvent dispersion to the greatest extent.

[0059] In some embodiments, the stirring time in step one can be selected as 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.

[0060] In some embodiments, the stirring time for mixing the gel with the water-based organic solvent in Step 2 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. The stirring time after introducing the organic modifier in Step 2 can be selected from 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, or a value within the range formed by any two of the above values.

[0061] 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.

[0062] In this application, the complex dispersion containing the π-conjugated conductive polymer and the polyanion is subjected to short-term treatment, and at the same time, an organic modifier is introduced, and a highly conductive polymer complex organic solvent dispersion can be obtained without heating, which greatly saves the production cost.

[0063] 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.

[0064] 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-hexoxypyrrole), poly(3-methyl-4-hexoxypyrrole).

[0065] 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-dodecyloxythiophene), poly(3-octadecyloxythiophene), 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-didodecyloxythiophene), 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).

[0066] 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).

[0067] In some embodiments, the polyanions include sulfonic polymers and carboxylic polymers, preferably sulfonic polymers.

[0068] In some embodiments, the sulfonic polymers 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).

[0069] In some embodiments, the carboxylic 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).

[0070] 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.

[0071] In some embodiments, the aqueous organic solvent includes at least one of an alcohol solvent, a ketone solvent, and an ester solvent.

[0072] The alcohol solvent, the ketone solvent, and the ester solvent can all accelerate the formation of precipitation.

[0073] In some embodiments, the aqueous organic solvent includes at least one of an alcohol solvent and an ester solvent.

[0074] The alcohol solvent and the ester solvent can both achieve the acceleration of precipitation formation, and compared with a ketone solvent such as methyl ethyl ketone, the alcohol solvent and the ester solvent are safer, non-toxic, and beneficial to environmental protection.

[0075] In some embodiments, the first organic solvent includes an alcohol solvent.

[0076] In some embodiments, the second organic solvent includes an alcohol solvent.

[0077] In some embodiments, the alcohol solvent includes at least one of methanol, ethanol, isopropanol, n-butanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, cyclohexanol, octanol, allyl alcohol.

[0078] In some embodiments, the ketone solvent includes 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.

[0079] In some embodiments, the ester solvent includes at least one of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.

[0080] In some embodiments, the organic modifier includes at least one of an organic amine compound and an epoxy compound.

[0081] In some embodiments, the organic amine compound includes at least one of octylamine, aniline, toluidine, benzylamine, ethanolamine, diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine, triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine.

[0082] In some embodiments, the epoxy compounds include at least one of ethylene oxide, propylene oxide, 2,3-epoxybutane, epoxybutane, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, ethyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 1,2-epoxyeicosane, 2-(chloromethyl)-1,2-epoxypropane, glycidol, epichlorohydrin, epibromohydrin, butyl glycidyl ether, 1,2-epoxyhexane, 1,2-epoxy-9-decane, 2-(chloromethyl)-1,2-epoxybutane, 2-ethylhexyl glycidyl ether, 1,2-epoxy-1H,1H,2H,2H,3H,3H-trifluorobutane, allyl glycidyl ether, tetracyanoethylene oxide, glycidyl butyrate, 1,2-epoxycyclooctane, glycidyl methacrylate, 1,2-epoxycyclododecane, 1-methyl-1,2-epoxycyclohexane, 1,2-epoxycyclopentadecane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxy-1H,1H,2H,2H,3H,3H-heptadecafluorobutane, 3,4-epoxytetrahydrofuran, glycidyl stearate.

[0083] The above-mentioned organic modifiers can all achieve surface modification of the composite containing the π-conjugated conductive polymer and the polyanion to prepare the organic solvent dispersion of the highly conductive polymer composite.

[0084] In some embodiments, the pressure of the high-pressure homogenizer is 200 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 from 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 the values in the range formed by any two of the above values, and the number of homogenization times of the high-pressure homogenizer can be selected from 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, or the values in the range formed by any two of the above values.

[0085] In some embodiments, the mass ratio of the composite dispersion to the long-chain alkylbenzenesulfonic acid is (15 to 25):1. In some embodiments, the mass ratio of the composite dispersion to the long-chain alkylbenzenesulfonic acid is 15:1, 16:1, 18:1, 20:1, 22:1, 24:1, 25:1, or the ratio in the range formed by any two of the above ratios.

[0086] The mass ratio of the complex dispersion liquid to the long-chain alkylbenzenesulfonic acid is (15 - 25):1, which can not only provide enough long-chain alkylbenzenesulfonic acid for mixing with the complex dispersion liquid, but also avoid the influence of excessive long-chain alkylbenzenesulfonic acid on the dispersion stability of the complex containing the π-conjugated conductive polymer and polyanion in the subsequent second organic solvent after modification.

[0087] In some embodiments, the mass ratio of the complex dispersion liquid to the aqueous organic solvent is 1:(1.5 - 3). In some embodiments, the mass ratio of the complex dispersion liquid to the aqueous 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.

[0088] Controlling the mass ratio of the complex dispersion liquid to the aqueous organic solvent to be 1:(1.5 - 3) can provide enough aqueous organic solvent to accelerate the precipitation of the precipitate in the mixture, and at the same time can further improve the conductivity of the high-conductive polymer complex.

[0089] In some embodiments, the mass ratio of the complex dispersion liquid to the organic modifier is (30 - 100):1. In some embodiments, the mass ratio of the complex dispersion liquid to the organic modifier is 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, or a ratio within the range formed by any two of the above ratios.

[0090] Controlling the mass ratio of the complex dispersion liquid to the organic modifier to be (30 - 100):1 can provide enough organic modifier to achieve surface modification of the complex containing the π-conjugated conductive polymer and polyanion, so as to prepare a high-conductive polymer complex organic solvent dispersion liquid with high dispersion stability and high light transmittance.

[0091] In some embodiments, the solid content of the high-conductive polymer complex dispersion liquid is 0.5% - 1.5%. In some embodiments, the solid content of the high-conductive polymer complex dispersion liquid 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.

[0092] In some embodiments, the average particle size of the highly conductive polymer composite dispersion is 50 nm to 130 nm, and the PI value is 0.2 to 0.45. In some embodiments, the average particle size of the highly conductive polymer composite dispersion 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, or a value within the range formed by any two of the above values, and the PI value can be selected from 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, or a value within the range formed by any two of the above values.

[0093] The average particle size of the highly conductive polymer composite organic solvent dispersion prepared in this application is not higher than 130 nm, and the PI value is 0.2 to 0.45, which is beneficial to improving the stability of the highly conductive polymer composite organic solvent dispersion and the conductive performance of its film formation.

[0094] In some embodiments, the gel is mixed with an aqueous organic solvent and stirred at room temperature for 1 min to 10 min; then an organic modifier is added and stirred at room temperature for 10 min to 60 min. The obtained mixture specifically includes:

[0095] The gel is mixed with a first aqueous organic solvent and stirred at room temperature for 1 min to 5 min, then a second aqueous organic solvent is added and stirred at room temperature for 1 min to 5 min; then an organic modifier is added and stirred at room temperature for 10 min to 60 min to obtain a mixture;

[0096] Among them, 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.

[0097] The precipitate formed after sequentially adding the first aqueous organic solvent and the second aqueous organic solvent and stirring for several minutes can be quickly filtered.

[0098] In some embodiments, the gel is mixed with an aqueous organic solvent and stirred at room temperature for 1 min to 10 min; then an organic modifier is added and stirred at room temperature for 10 min to 60 min. The obtained mixture specifically includes:

[0099] The gel is mixed with an alcohol solvent and stirred at room temperature for 1 min to 5 min; then an organic modifier is added and stirred at room temperature for 10 min to 60 min to obtain a mixture.

[0100] Compared with sequentially adding the first aqueous organic solvent and the second aqueous organic solvent, the average particle size of the precipitate formed after adding the alcohol solvent in one step is relatively lower, which is beneficial to preparing an organic solvent dispersion with a smaller average particle size.

[0101] 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) dispersion (PEDOT-PAS).

[0102] The present application provides a method for preparing a high-conductive polymer composite organic solvent dispersion, which includes:

[0103] Step 1: 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 3 min to 10 min to obtain a gel;

[0104] 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;

[0105] Step 3: Filter the mixture, take the precipitate and mix it with a first organic solvent, stir at room temperature for 1 min to 5 min, and filter again to obtain a high-conductive polymer composite;

[0106] Step 4: Mix the high-conductive polymer composite, an organic modifier, and a second organic solvent, and perform homogenization under a high-pressure homogenizer to obtain a high-conductive polymer composite organic solvent dispersion.

[0107] It is found that the organic modifier can also be introduced during the high-pressure homogenization process to achieve surface modification of the high-conductive polymer composite, that is, the high-conductive polymer composite and the organic modifier are homogenized under a high-pressure homogenizer to obtain a high-conductive polymer composite organic solvent dispersion. This organic solvent has excellent stability and high light transmittance, and the surface resistance of the film layer prepared from the high-conductive polymer composite organic solvent dispersion is also as low as 10 4 Ω / □, greatly broadening its application window.

[0108] The present application provides a method for preparing a high-conductive polymer composite, which includes:

[0109] 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 3 min to 10 min to obtain a gel;

[0110] Mix the gel with an aqueous organic solvent, stir at room temperature for 1 min to 10 min, then add an organic modifier, and stir at room temperature for 10 min to 60 min to obtain a mixture;

[0111] Filter the mixture, take the precipitate and mix it with an organic solvent, stir at room temperature for 1 min to 5 min, and filter again to obtain a highly conductive polymer composite.

[0112] In some embodiments, the organic solvent includes an alcohol solvent.

[0113] This application provides an antistatic liquid, which includes a resin, a solvent, an auxiliary agent, and a dispersion of a highly conductive polymer composite in an organic solvent prepared by the preparation method in some embodiments;

[0114] Based on the total mass of the antistatic liquid, the mass content of the resin is 2% to 10%, the mass content of the solvent is 15% to 35%, and the mass content of the dispersion of the highly conductive polymer composite in the organic solvent is 55% to 80%.

[0115] In some embodiments, based on the total mass of the antistatic liquid, the mass content of the resin can be selected from 2%, 3%, 4%, 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 selected from 15%, 17%, 19%, 21%, 23%, 25%, 27%, 29%, 31%, 33%, 35%, or a value within the range formed by any two of the above values; the mass content of the dispersion of the highly conductive polymer composite in the organic solvent can be selected from 55%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, or a value within the range formed by any two of the above values.

[0116] This application provides the application of a dispersion of a highly conductive polymer composite in an organic solvent prepared by the preparation method in some embodiments in flexible electronic devices and sensors.

[0117] Examples

[0118] The following examples are for better further understanding of the present invention, are not limited to the best embodiment, and do not constitute a limitation to 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 the art can be followed. For the reagents or instruments where the manufacturers are not indicated, they are all conventional reagent products that can be obtained through commercial purchase.

[0119] I. Preparation method

[0120] Example 1

[0121] Preparation of the dispersion of the highly conductive polymer composite in the organic solvent:

[0122] 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 below) and dodecylbenzenesulfonic acid in a beaker at a mass ratio of 20:1, and stir at 600 rpm for 6 min to obtain a gel.

[0123] Step 2: Add the above gel to isopropanol (the mass ratio of the PEDOT-PSS composite dispersion to isopropanol is 1:2), and stir at 600 rpm for 2 min; then add trioctylamine (the mass ratio of the PEDOT-PSS composite dispersion to trioctylamine is 50:1), and stir at 600 rpm for 30 min to obtain a mixture.

[0124] 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 rpm for 2 min, and filter again to obtain a highly conductive polymer composite.

[0125] Step 4: Mix the above highly conductive polymer composite and isopropanol and homogenize it under a high-pressure homogenizer at a pressure of 400 bar for 3 times to obtain a highly conductive PEDOT-PSS organic solvent dispersion with a solid content of 0.9%.

[0126] Preparation of the antistatic liquid: Mix the above highly conductive PEDOT-PSS organic solvent dispersion, acrylate resin, and isopropanol at a mass ratio of 6:0.3:2.1 to prepare the antistatic liquid.

[0127] Examples 2 - 3

[0128] The preparation of the highly conductive polymer composite organic solvent dispersion and the antistatic liquid in Examples 2 - 3 is similar to that in Example 1, except that dodecylbenzenesulfonic acid, the raw material for preparing the highly conductive polymer composite organic solvent dispersion in Example 1, is adjusted to decylbenzenesulfonic acid and hexadecylbenzenesulfonic acid respectively, as shown in Tables 1 and 2 specifically.

[0129] Examples 4 - 5

[0130] The preparation of the highly conductive polymer composite organic solvent dispersion and the antistatic liquid in Examples 4 - 5 is similar to that in Example 1, except that isopropanol, the raw material for preparing the highly conductive polymer composite organic solvent dispersion in Example 1, is adjusted to ethyl acetate and methanol respectively, as shown in Tables 1 and 2 specifically.

[0131] Example 6

[0132] The preparation of the organic solvent dispersion of the highly conductive polymer composite in Example 6 and the antistatic liquid are similar to those in Example 1, except that: isopropanol, the raw material for preparing the organic solvent dispersion of the highly conductive polymer composite in Example 1, is respectively adjusted to methyl isobutyl ketone + isopropanol. The specific steps are as follows:

[0133] Step 1: Place the PEDOT-PSS composite dispersion and dodecylbenzenesulfonic acid in a beaker according to a mass ratio of 25:1, and stir at 600 rpm for 6 min to obtain a gel.

[0134] Step 2: Add the above gel to methyl isobutyl ketone (the mass ratio of the PEDOT-PSS composite dispersion to methyl isobutyl ketone is 1:2), stir at 600 rpm for 2 min, then add isopropanol (the mass ratio of the PEDOT-PSS composite dispersion to isopropanol is 1:2), and stir at 600 rpm for 2 min; then add trioctylamine (the mass ratio of the PEDOT-PSS composite dispersion to trioctylamine is 50:1), and stir at 600 rpm for 30 min to obtain a mixture.

[0135] 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 rpm for 2 min, and filter again to obtain a highly conductive polymer composite.

[0136] Step 4: Mix the above highly conductive polymer composite and isopropanol 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%.

[0137] Preparation of the antistatic liquid: Mix the above highly conductive PEDOT-PSS dispersion, organic solvent-based acrylate resin, and isopropanol according to a mass ratio of 6:0.3:2.1 to prepare the antistatic liquid.

[0138] Examples 7 - 9

[0139] The preparation of the organic solvent dispersion of the highly conductive polymer composite in Examples 7 - 9 and the antistatic liquid are similar to those in Example 1, except that: trioctylamine, the raw material for preparing the organic solvent dispersion of the highly conductive polymer composite in Example 1, is respectively adjusted to ethanolamine, diphenylamine, and 1,2-epoxybutane.

[0140] Examples 10 - 11

[0141] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 10 to 11 are similar to those in Example 1, except that the mass ratio of the composite dispersion to long-chain alkylbenzenesulfonic acid in the preparation of the organic solvent dispersion of the highly conductive polymer composite in Example 1 is adjusted to 15:1 and 25:1 respectively.

[0142] Examples 12 to 13

[0143] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 12 to 13 are similar to those in Example 1, except that the stirring time in Step 1 of the preparation of the organic solvent dispersion of the highly conductive polymer composite in Example 1 is adjusted to 3 min and 10 min respectively.

[0144] Examples 14 to 15

[0145] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 14 to 15 are similar to those in Example 1, except that the stirring time of the organic modifier in Step 2 of the preparation of the organic solvent dispersion of the highly conductive polymer composite in Example 1 is adjusted to 10 min and 1 h respectively.

[0146] Examples 16 to 17

[0147] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 16 to 17 are similar to those in Example 1, except that the mass ratio of the PEDOT-PSS composite dispersion to trioctylamine in the preparation of the organic solvent dispersion of the highly conductive polymer composite in Example 1 is adjusted to 30:1 and 100:1 respectively.

[0148] Examples 18 to 19

[0149] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 18 to 19 are similar to those in Example 1, except that the pressure of the high-pressure homogenizer in the preparation of the organic solvent dispersion of the highly conductive polymer composite in Example 1 is adjusted to 200 bar and 800 bar respectively.

[0150] Examples 20 to 21

[0151] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 20 to 21 are similar to those in Example 1, except that the solid content of the organic solvent dispersion of the highly conductive polymer composite prepared in Example 1 is adjusted to 0.5% and 1.5% respectively.

[0152] Examples 22 to 23

[0153] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 22 to 23 are similar to those in Example 1, except that the mass content of the organic solvent dispersion of the highly conductive polymer composite in the antistatic liquid in Example 1 is adjusted to 55% and 80% respectively (the content of other substances is reduced proportionally to achieve the adjustment of the mass content of the organic solvent dispersion of the highly conductive polymer composite).

[0154] Examples 24 to 26

[0155] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Examples 24 to 26 are similar to those in Example 1, except that the raw material PEDOT-PSS composite dispersion for preparing the organic solvent dispersion of the highly conductive polymer composite in Example 1 is adjusted to PPy-PSS composite dispersion (purchased from Shanghai Macklin Biochemical Co., Ltd., solid content 1.3%), PANI-PSS composite dispersion (purchased from Shanghai Macklin Biochemical Co., Ltd., solid content 1.5%), PEDOT-PVS composite dispersion (purchased from Shanghai Ouyi Organic Optoelectronic Materials Co., Ltd., solid content 1.3%) respectively. See Tables 1 and 2 for details.

[0156] Example 27

[0157] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Example 27 are similar to those in Example 1, except that the addition sequence of the organic modifier trioctylamine in the preparation of the organic solvent dispersion of the highly conductive polymer composite in Example 1 is adjusted. The specific steps are as follows:

[0158] Step 1: Place the PEDOT-PSS composite dispersion and dodecylbenzenesulfonic acid in a beaker at a mass ratio of 20:1, stir at 600 rpm for 6 min to obtain a gel;

[0159] Step 2: Add the above gel to isopropanol (the mass ratio of PEDOT-PSS composite dispersion to isopropanol is 1:2), stir at 600 rpm for 2 min to obtain a mixture;

[0160] 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 rpm for 2 min, and filter again to obtain a highly conductive polymer composite;

[0161] Step 4: Mix the above highly conductive polymer composite, trioctylamine and isopropanol and homogenize them under a high-pressure homogenizer at a pressure of 400 bar for 3 times to obtain a highly conductive PEDOT-PSS organic solvent dispersion with a solid content of 0.9%. Among them, the mass ratio of the PEDOT-PSS composite dispersion to trioctylamine is 50:1.

[0162] Comparative Example

[0163] Comparative Example 1

[0164] The preparation of the organic solvent dispersion of the highly conductive polymer composite in Comparative Example 1 and the antistatic liquid are similar to those in Example 1, except that: dodecylbenzenesulfonic acid, the raw material for preparing the organic solvent dispersion of the highly conductive polymer composite in Example 1, is not introduced. The specific steps are as follows:

[0165] Put the PEDOT-PSS composite dispersion, isopropanol, and trioctylamine in a beaker according to a mass ratio of 50:100:1, stir at 600 rpm for 1 h, and no gel is obtained; filtering the mixture fails to obtain a precipitate, and the experiment is aborted.

[0166] Comparative Example 2

[0167] The preparation of the organic solvent dispersion of the highly conductive polymer composite in Comparative Example 2 and the antistatic liquid are similar to those in Example 1, except that: dodecylbenzenesulfonic acid, the raw material for preparing the organic solvent dispersion of the highly conductive polymer composite in Example 1, is adjusted to p-toluenesulfonic acid. The specific steps are as follows:

[0168] Put the PEDOT-PSS composite dispersion and p-toluenesulfonic acid in a beaker according to a mass ratio of 25:1, stir at 600 rpm for 1 h, and no gel is obtained;

[0169] Add isopropanol to the above solution (the mass ratio of the PEDOT-PSS composite dispersion to isopropanol is 1:2), stir at 600 rpm for 1 h; then add trioctylamine organic modifier (the mass ratio of the PEDOT-PSS composite dispersion to trioctylamine is 50:1), stir at 600 rpm for 1 h to obtain a mixture;

[0170] Filter the above mixture and no precipitate is obtained, and the experiment is aborted.

[0171] Comparative Example 3

[0172] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Comparative Example 3 are similar to those in Example 1, except that dodecylbenzenesulfonic acid, the raw material for preparing the organic solvent dispersion of the highly conductive polymer composite in Example 1, is not introduced. The specific steps are as follows:

[0173] Put the PEDOT-PSS composite dispersion, methanol, and methyl ethyl ketone in a beaker according to a mass ratio of 100:12.5:200, stir at 600 rpm at 70 °C for 4 h, and obtain a precipitate after standing;

[0174] Add trioctylamine organic modifier to the precipitate solution (the mass ratio of the PEDOT-PSS composite dispersion to trioctylamine is 50:1), and stir at 600 rpm at room temperature for 30 min to obtain a mixture;

[0175] Filter the 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 rpm for 2 min, and filter again to obtain a conductive polymer composite;

[0176] Mix the above highly conductive polymer composite and isopropanol and homogenize them 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%.

[0177] Comparative Example 4

[0178] The preparation of the organic solvent dispersion of the highly conductive polymer composite and the antistatic liquid in Comparative Example 4 are similar to those in Example 1, except that dodecylbenzenesulfonic acid, the raw material for preparing the organic solvent dispersion of the highly conductive polymer composite in Example 1, is not introduced. The specific steps are as follows:

[0179] Put the PEDOT-PSS composite dispersion and methyl ethyl ketone in a beaker according to a mass ratio of 1:2, stir at 600 rmp at 70 °C for 6 h, and no precipitate is obtained;

[0180] Add trioctylamine organic modifier to the above system (the mass ratio of the PEDOT-PSS composite dispersion to trioctylamine is 50:1), and stir at 600 rpm at room temperature for 30 min;

[0181] Then homogenize the above system 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 0.45%.

[0182] Table 1 Preparation Parameters of Organic Solvent Dispersions of High Conductive Polymer Composites

[0183]

[0184]

[0185] Table 2 Preparation Parameters of Organic Solvent Dispersions of High Conductive Polymer Composites

[0186]

[0187]

[0188] II. Test Methods

[0189] 1) Testing of the average particle size, PI value, and potential of the organic solvent dispersion of the high conductive polymer composite

[0190] Refer to the standard of GB / T 19077.1-2003 for testing the average particle size of the modified nanoparticles. Use a Horiba SZ-100V2 nanoparticle size analyzer to test the organic solvent dispersion of the high conductive polymer composite, obtain the particle size distribution curve of the organic solvent dispersion of the high conductive polymer composite, and directly obtain the average particle size and PI value of the organic solvent dispersion of the high conductive polymer composite from the particle size distribution curve.

[0191] 2) Testing of the surface resistance of the film layer formed from the organic solvent dispersion of the high conductive polymer composite

[0192] Film formation of the organic solvent dispersion of the high conductive polymer composite: Coat the organic solvent dispersion of the high conductive polymer composite to be tested on a corona-treated PET substrate using a #6 wire bar, and dry it in an oven at 120 °C for 1 minute to obtain its film layer.

[0193] Use a surface resistance device to test the surface resistance properties of the film layer sample prepared by coating the above-mentioned organic solvent dispersion of the high conductive polymer composite. The model of the test device is the SIMCO ST-4 surface resistance meter.

[0194] 3) Testing of the light transmittance of the film layer formed from the organic solvent dispersion of the high conductive polymer composite

[0195] Film formation of the organic solvent dispersion of the high conductive polymer composite: Coat the organic solvent dispersion of the high conductive polymer composite to be tested on a corona-treated PET substrate using a #6 wire bar, and dry it in an oven at 120 °C for 1 minute to obtain its film layer.

[0196] The light transmittance of the optical film was tested according to the GB / T 2410-2008 standard. The prepared film layer was tested for transmittance in the range of 400 nm to 800 nm using a UV-Vis spectrophotometer, and the model of the test equipment was Shimadzu UV-1800.

[0197] 4) Test of the surface resistance after film formation of the antistatic liquid

[0198] Film formation of the antistatic liquid: Using isopropanol as a diluent, the antistatic liquid to be tested was diluted 1:10, and then 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.

[0199] The surface resistance properties of the film layer sample prepared by coating the above antistatic liquid were tested using a surface resistance equipment, and the model of the test equipment was SIMCO ST-4 surface resistance meter.

[0200] Table 3 Performance parameters of each example and comparative example

[0201]

[0202]

[0203] III. Analysis of test results of each example and comparative example

[0204] As can be seen from Examples 1 to 27 and Comparative Examples 1 to 4, the preparation method of the present application is simple in operation, short in time-consuming, and can realize the preparation of a highly conductive polymer composite with surface modification without heating. Moreover, the average particle size of its organic solvent dispersion is lower than 130 nm, and the PI value is not higher than 0.45, which is beneficial to improving the dispersion stability of the organic solvent dispersion. And the organic solvent dispersion of the highly conductive polymer composite has a high light transmittance. More importantly, the organic solvent dispersion of the highly conductive polymer composite and its antistatic liquid coating film both have a low surface resistance, that is, excellent conductive performance.

[0205] As can be seen from Examples 1 to 3 and Comparative Examples 1 to 2, the introduction of long-chain alkylbenzenesulfonic acid is very crucial for the gelation and precipitation formation of the PEDOT-PSS dispersion. Under the action of long-chain alkylbenzenesulfonic acid, the non-conductive PSS component in the PEDOT-PSS composite can be partially stripped, thereby improving the conductive performance of the PEDOT-PSS composite. At the same time, the introduction of an organic modifier can react with the sulfonic acid group in PSS. After modification, the highly conductive PEDOT-PSS polymer composite can be well dispersed in isopropanol to obtain a highly conductive PEDOT-PSS organic solvent dispersion with excellent dispersion stability.

[0206] As can be seen from Examples 1 to 3 and Comparative Examples 3 to 4, compared with the treatment of the PEDOT-PSS complex with alcohol solvents / ketone solvents, the treatment of the 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 help to further improve its electrical conductivity.

[0207] As can be seen from Example 1 and Examples 4 to 6, alcohol solvents, ester solvents or ketone solvents can all achieve the formation of accelerated precipitation, and can all achieve high dispersion stability of the highly conductive PEDOT-PSS aqueous dispersion and its high electrical conductivity. As can be seen from Example 1 and Example 6, the precipitate generated by the two-step method is larger, so the filtration speed is faster, further saving production time.

[0208] As can be seen from Example 1 and Examples 7 to 9, the organic modifier can be an organic amine compound or an epoxy compound, and the PEDOT-PSS organic solvent dispersion after surface modification all has high electrical conductivity.

[0209] As can be seen from Example 1 and Examples 10 to 17, in the process of gel formation and modification of the PEDOT-PSS dispersion, the selection of a suitable long-chain alkylbenzenesulfonic acid, the appropriate amount of the organic modifier and the appropriate stirring time are used to strip the PSS component in PEDOT-PSS to a certain extent and make the organic amine compound / epoxy compound and the sulfonic acid group in PSS react fully, which is beneficial to improving the dispersion stability and electrical conductivity of the PEDOT-PSS organic solvent dispersion.

[0210] As can be seen from Example 1 and Examples 18 to 21, high-pressure homogenization of the PEDOT-PSS organic solvent dispersion is relatively easy. However, when the homogenization pressure or the solid content of the dispersion is too high, the electrical conductivity of its organic solvent dispersion, especially the film conductivity of its antistatic liquid, decreases.

[0211] As can be seen from Example 1 and Examples 22 to 23, when the content of the PEDOT-PSS organic solvent dispersion in the antistatic liquid decreases or increases, the film resistance of the antistatic liquid also increases or decreases accordingly.

[0212] As can be seen from Example 1 and Examples 24 to 26, 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 its organic solvent dispersion have a lower average particle size and PI value, as well as high film conductivity.

[0213] As can be seen from Example 1 and Example 27, the addition of the organic modifier can also be carried out in the homogenization step, and the properties of the obtained organic solvent dispersion are similar to those of the PEDOT-PSS organic solvent dispersion obtained by introducing the organic modifier during the precipitation process.

[0214] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended 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 for 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 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 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 falling within the scope of the claims.

Claims

1. A method for preparing a highly conductive polymer composite organic solvent dispersion, 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 3 to 10 minutes to obtain a gel; Step 2: mixing the gel with an aqueous organic solvent, stirring at room temperature for 1 to 10 minutes; then adding an organic modifier, stirring at room temperature for 10 to 60 minutes, to obtain a mixture; Step 3: filtering the mixture, taking the precipitate and mixing it with the first organic solvent, stirring at room temperature for 1 min to 5 min, and filtering again to obtain a highly conductive polymer composite; Step 4: Mix the highly conductive polymer composite and the second organic solvent, and homogenize them in a high-pressure homogenizer to obtain an organic solvent dispersion of the highly conductive polymer composite.

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, and optionally comprises a sulfonic polymer; or The long-chain alkylbenzene sulfonic acid includes C 10-16 At least one of alkylbenzene sulfonic acids; and / or The aqueous organic solvent includes at least one of an alcohol solvent, a ketone solvent, and an ester solvent, and optionally includes at least one of an alcohol solvent and an ester solvent; and / or The first organic solvent comprises an alcohol solvent; and / or The second organic solvent comprises an alcohol solvent; and / or The organic modifier includes at least one of an organic amine compound and an epoxy compound; and / or The pressure of the high-pressure homogenizer is 200 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 aqueous complex dispersion to the long-chain alkylbenzene sulfonic acid is (15-25):1; and / or The mass ratio of the composite dispersion to the aqueous organic solvent is 1:(1.5-3); and / or The mass ratio of the composite dispersion to the organic modifier is (30-100):1; and / or The solid content of the highly conductive polymer composite organic solvent dispersion is 0.5% to 1.5%, and can be optionally 0.5% to 1%; and / or The average particle size of the highly conductive polymer composite organic solvent dispersion is 50 nm to 130 nm, and may be 70 nm to 120 nm, and the PI is 0.2 to 0.45, and may be 0.25 to 0.

4.

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; then an organic modifier is added and stirred at room temperature for 10 to 60 minutes to obtain a mixture, which specifically includes: The gel is mixed with a first aqueous organic solvent, stirred at room temperature for 1 to 5 minutes, and then a second aqueous organic solvent is added, stirred at room temperature for 1 to 5 minutes; then an organic modifier is added, and stirred at room temperature for 10 to 60 minutes to obtain the mixture, wherein 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; or The gel is mixed with an alcohol solvent and stirred at room temperature for 1 to 5 minutes; then an organic modifier is added and stirred at room temperature for 10 to 60 minutes to obtain the mixture.

5. The preparation method according to any one of claims 1 to 4, 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; and / or The organic amine compound includes at least one of octylamine, aniline, toluidine, benzylamine, ethanolamine, diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, dinaphthylamine, triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine and trinaphthylamine; the epoxy compound includes ethylene oxide, propylene oxide, 2,3-butylene oxide, butylene oxide, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxypentane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydecane and 1,3-epoxybutylene oxide. At least one of 3-butadiene monoxide, 1,2-epoxytetradecane, glycidyl methyl ether, 1,2-epoxyoctadecane, 1,2-epoxyhexadecane, 1,2-epoxyeicosane, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, p-tert-butylphenyl glycidyl ether, o-cresyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, carbon dodecyl glycidyl ether, cardanol glycidyl ether, 1,2-epoxy-4-vinylcyclohexane, and diallyl monoglycidyl isocyanurate.

6. The preparation method according to any one of claims 1 to 4, 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.

7. A method for preparing a highly conductive polymer composite organic solvent dispersion, 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 3 to 10 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 first organic solvent, stirring at room temperature for 1 min to 5 min, and filtering again to obtain a highly conductive polymer composite; Step 4: Mix the highly conductive polymer composite, the organic modifier and the second organic solvent, and homogenize them in a high-pressure homogenizer to obtain the highly conductive polymer composite organic solvent 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 3 to 10 minutes to obtain a gel; The gel is mixed with an aqueous organic solvent and stirred at room temperature for 1 to 10 minutes; then an organic modifier is added and stirred at room temperature for 10 to 60 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 organic solvent dispersion comprising a resin, a solvent 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 2% to 10%, the mass content of the solvent is 15% to 35%, and the mass content of the highly conductive polymer composite organic solvent dispersion is 55% to 80%.

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

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