CN112795144A - Aqueous dispersion containing conductive polymer and process for producing the same - Google Patents
Aqueous dispersion containing conductive polymer and process for producing the same Download PDFInfo
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Abstract
The present disclosure provides an aqueous dispersion comprising a conductive polymer and a dispersed phase dispersed in water, wherein the dispersed phase is formed by combining the conductive polymer and a dispersed dopant through ionic interaction, the molar mass ratio of the conductive polymer to the dispersed dopant is 1: 1 to 1: 4, the conductive polymer is P (AZ-co-EDOT), the dispersed dopant is polystyrene sulfonate (PSS), the dispersed phase is formed by in-situ polymerization of Azulene (AZ) monomers and 3, 4-Ethylenedioxythiophene (EDOT) monomers with the dispersed dopant, the conductivity of the aqueous dispersion is adjustable, and the conductivity of the aqueous dispersion is adjusted by adjusting the ratio of the AZ monomers to the EDOT monomers. According to the present disclosure, it is possible to provide an aqueous dispersion containing a conductive polymer having a high seebeck coefficient and adjustable conductivity and a method for preparing the same.
Description
Technical Field
The present disclosure generally relates to an aqueous dispersion containing a conductive polymer and a method for preparing the same.
Background
In recent years, thermoelectric materials have a wide application prospect in the field of energy as functional materials capable of converting heat energy and electric energy into each other. Conventional thermoelectric materials are typically inorganic materials such as bismuth telluride and alloys thereof, lead telluride and alloys thereof, and silicon germanium alloys, among others. However, since telluride is toxic and generally limited in practical applications, research on thermoelectric materials is beginning to expand in the direction of graphene, nanomaterials, conductive polymers, and the like. The conductive polymer has the characteristics of high conductivity, easiness in processing, flexibility and the like, and can meet different application requirements in the thermoelectric field. For example, a polymer film made of a conductive polymer may be overlaid on a substrate or other thermoelectric device to form a flexible thermoelectric device.
At present, common conductive polymers include polyacetylene, polythiophene, polypyrrole, polyaniline, polyphenylene ethylene, polydiyne and the like, but the conductive polymers often have a small seebeck coefficient and generally cannot show high thermoelectric efficiency in the application of the thermoelectric field. Therefore, research into conductive polymer materials having a high seebeck coefficient is imperative.
Disclosure of Invention
The present disclosure has been made in view of the above-mentioned state of the art, and an object thereof is to provide an aqueous dispersion containing a conductive polymer having a high seebeck coefficient and adjustable conductivity, and a method for preparing the same.
To this end, the present disclosure provides, in one aspect, an aqueous dispersion comprising an electrically conductive polymer, and a dispersed phase dispersed in water, the dispersed phase being formed by ionic interaction of the electrically conductive polymer with a dispersed dopant, the molar mass ratio of the electrically conductive polymer to the dispersed dopant being from 1: 1 to 1: 4, the electrically conductive polymer being P (AZ-co-EDOT), the dispersed dopant being polystyrene sulfonate (PSS), the P (AZ-co-EDOT) having a structure as shown in fig. 1, wherein n is an integer greater than zero, and x is a number greater than zero and less than 1; and the disperse phase is formed by in-situ polymerization of an Azulene (AZ) monomer, a 3, 4-Ethylenedioxythiophene (EDOT) monomer and a disperse dopant, the conductivity of the aqueous dispersion is adjustable, and the conductivity of the aqueous dispersion is adjusted by adjusting the ratio of the AZ monomer to the EDOT monomer. In the present disclosure, AZ monomer and EDOT monomer can be polymerized to form P (AZ-co-EDOT) conductive polymer having a stable electron donor-acceptor structure, and the electrical conductivity of the aqueous dispersion can be adjusted by adjusting the ratio of AZ monomer to EDOT monomer, the water dispersibility of P (AZ-co-EDOT) can be enhanced by PSS, and the ionic interaction between P (AZ-co-EDOT) and PSS can form a huge seebeck effect, resulting in an aqueous dispersion having a high seebeck coefficient.
Further, in an aqueous dispersion according to an aspect of the present disclosure, optionally, the particle size of the dispersed phase is 0.5 μm to 2 μm. This can enhance the conductivity of the aqueous dispersion.
Further, in an aqueous dispersion according to an aspect of the present disclosure, optionally, the molar mass ratio of the AZ monomer to the EDOT monomer is 10: 1 to 1: 10. thus, aqueous dispersions of different conductivities can be obtained.
Further, in an aqueous dispersion according to an aspect of the present disclosure, optionally, the electrical conductivity of the aqueous dispersion is 0.05S/cm to 0.45S/cm.
In addition, in the aqueous dispersion according to an aspect of the present disclosure, optionally, the aqueous dispersion has a seebeck coefficient of 1500 μ V/K to 2500 μ V/K. This can enhance the thermoelectric efficiency of the aqueous dispersion.
Another aspect of the present disclosure provides a method for preparing an aqueous dispersion containing a conductive polymer, comprising: 1) mixing a reaction monomer, a dispersed dopant and water to obtain a mixed solution, wherein the molar mass ratio of the AZ monomer to the EDOT monomer is 10: 1 to 1: 10, the reaction monomers are Azulene (AZ) monomers and 3, 4-Ethylenedioxythiophene (EDOT) monomers, and the dispersing dopant is polystyrene sulfonate (PSS); 2) adding an oxidant and a catalyst to the mixed solution, and carrying out in-situ polymerization to obtain a reaction solution having a dispersed phase formed by combining a conductive polymer and a dispersed dopant through ionic interaction, wherein the molar mass ratio of the conductive polymer to the dispersed dopant is 1: 1 to 1: 4; and 3) removing inorganic salts in the reaction solution, and filtering to obtain an aqueous dispersion containing a conductive polymer, wherein the conductivity of the aqueous dispersion is adjusted by adjusting the ratio of the AZ monomer to the EDOT monomer, the conductive polymer is P (AZ-co-EDOT), the structural formula of the P (AZ-co-EDOT) is shown in figure 1, wherein n is an integer larger than zero, and x is a number larger than zero and smaller than 1. In the present disclosure, a P (AZ-co-EDOT) conductive polymer having a stable electron donor-acceptor structure is formed by polymerizing an AZ monomer and an EDOT monomer, and the conductivity of an aqueous dispersion can be adjusted by adjusting the ratio of the AZ monomer to the EDOT monomer, PSS is used as a dispersion dopant to enhance the water dispersibility of P (AZ-co-EDOT), and the ionic interaction between P (AZ-co-EDOT) and PSS can form a huge seebeck effect, whereby an aqueous dispersion having a high seebeck coefficient can be obtained.
In addition, in the preparation method according to an aspect of the present disclosure, optionally, the oxidizing agent is at least one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, and silver perchlorate, and the molar mass ratio of the reaction monomer to the oxidizing agent is 1: 1 to 1: 5. This can facilitate the progress of the polymerization reaction.
In addition, in the preparation method according to an aspect of the present disclosure, optionally, the catalyst is ferrous sulfate or ferric chloride, and the molar mass ratio of the reaction monomer to the catalyst is 1: 0.005 to 1: 0.015. This can facilitate the progress of the polymerization reaction.
In addition, in the preparation method according to an aspect of the present disclosure, optionally, a molar volume ratio (mol: L) of the reaction monomer to the water is 1: 10 to 1: 30. This can contribute to the dispersion of the conductive polymer and the progress of the polymerization reaction.
In addition, in the production method according to an aspect of the present disclosure, optionally, in step 3), the inorganic salt is removed using an anion and cation exchange resin, and filtration is performed using an ultrafiltration membrane, which is a polyvinylidene fluoride membrane. This enables the removal of inorganic salts and impurities in the reaction solution.
According to the present disclosure, it is possible to provide an aqueous dispersion containing a conductive polymer having a high seebeck coefficient and adjustable conductivity and a method for preparing the same.
Drawings
FIG. 1 shows the structural formula of P (AZ-co-EDOT).
FIG. 2 is a flow chart of a method for preparing an aqueous dispersion containing a conductive polymer.
Detailed Description
The present disclosure will be described in further detail with reference to the drawings and embodiments. In the drawings, the same components or components having the same functions are denoted by the same reference numerals, and redundant description thereof will be omitted.
In the present disclosure, the aqueous dispersion containing a conductive polymer may be simply referred to as an aqueous dispersion, and the method for producing the aqueous dispersion containing a conductive polymer may be simply referred to as a production method. The aqueous dispersion according to the present embodiment may be applied to a substrate by a method such as drop casting, spray coating, or layer-by-layer coating to form a polymer film. The substrate material may be a glass substrate or a metal base plate.
In some examples, the polymer film may be applied to a Liquid Crystal Display (LCD), a wearable thermoelectric device, a solar cell, a Light Emitting Diode (LED), an organic thin film transistor, or a biosensor.
In some examples, the aqueous dispersion may include water and a dispersed phase. Wherein the dispersed phase is dispersible in water. In addition, the water may be at least one of distilled water, deionized water, pure water, high purity water, and ultrapure water.
In some examples, the dispersed phase may be present in the aqueous dispersion in the form of particles (e.g., nanoparticles). In addition, the dispersed phase may be insoluble in water. In other examples, the dispersed phase may be slightly soluble in water.
In some examples, the particle size of the dispersed phase may be 0.5 μm to 2 μm. In this case, the dispersed phase can be stably and uniformly dispersed in water for a long period of time without causing an agglomeration phenomenon, whereby the conductivity of the aqueous dispersion can be enhanced.
In some examples, the dispersed phase may include a conductive polymer and a dispersed dopant. Thus, an aqueous dispersion containing a conductive polymer can be obtained. In addition, the conductive polymer may be combined with a dispersed dopant.
In some examples, the dispersed phase may be formed from a conductive polymer and a dispersed dopant. For example, the dispersed phase may be formed by the ionic interaction of the conductive polymer with the dispersed dopant. In some examples, the conductive polymer may be insoluble in water.
In some examples, the conductive polymer may include a copolymer. For example, the conductive polymer may be a mixture of a homopolymer and a copolymer, or may be a copolymer. In other examples, the conductive polymer may be an alternating copolymer (e.g., -A-B-, -AA-B-).
In some examples, the conductive polymer may be a copolymer formed from two monomers. In addition, in some examples, the conductive polymer may be formed from the polymerization of Azulene (AZ) with 3, 4-Ethylenedioxythiophene (EDOT). That is, the conductive polymer may be P (AZ-co-EDOT). In this case, since the EDOT molecule has good structural stability, the AZ monomer and the EDOT monomer can be polymerized to form a P (AZ-co-EDOT) conductive polymer having a stable electron donor-acceptor structure. This can enhance the stability of the aqueous dispersion.
In some examples, P (AZ-co-EDOT) has a structure as shown in fig. 1, wherein n is an integer greater than zero and x is a number greater than zero and less than 1. This can enhance the stability of the aqueous dispersion.
In some examples, the P (AZ-co-EDOT) conductivity may be adjusted by adjusting the ratio of AZ monomer to EDOT monomer. Thereby, the conductivity of the aqueous dispersion can be adjusted. In other words, the conductivity of the aqueous dispersion can be adjusted by adjusting the ratio of AZ monomer to EDOT monomer.
In some examples, in P (AZ-co-EDOT), the molar mass ratio of AZ monomer to EDOT monomer may be 10: 1 to 1: 10. thus, aqueous dispersions of different conductivities can be obtained.
In some examples, the molar mass ratio of AZ monomer to EDOT monomer may be 10: 1. 9: 1. 8: 2. 7: 3. 6: 4. 5: 5. 4: 6. 3: 7. 2: 8. 1: 9 or 1: 10.
in some examples, preferably, the molar mass ratio of AZ monomer to EDOT monomer may be 9:1 to 3: 7. This can further improve the thermoelectric efficiency of the aqueous dispersion.
In some examples, the conductive polymer may be a mixture including P (AZ-co-EDOT). For example, the conductive polymer may be a mixture of P (AZ-co-EDOT) and Polyazulene (PAZ), a mixture of P (AZ-co-EDOT) and poly 3, 4-ethylenedioxythiophene (PEDOT), or a mixture of P (AZ-co-EDOT), PAZ and PEDOT.
As described above, the dispersed phase may include dispersed dopants. In some examples, the dispersed phase may be polymerized in situ from a plurality of monomers (e.g., two) and a dispersed dopant. For example, the dispersed phase may be formed by in situ polymerisation of Azulene (AZ) monomers and 3, 4-Ethylenedioxythiophene (EDOT) monomers with a disperse dopant. Alternatively, the dispersed phase may be formed by in situ polymerization of a plurality of monomers (e.g., two) with a dispersed dopant in water.
In some examples, the dispersing dopant can be used to disperse the conductive polymer, altering the aqueous dispersion properties (e.g., seebeck coefficient, conductivity, transparency, etc.). In addition, the dispersed dopant may be soluble in water.
In some examples, the dispersed dopant may include a dispersant and a dopant. For example, the dispersant may include one or more of polystyrene sulfonate (PSS) or polystyrene sulfonic acid, and the dopant may include polystyrene sulfonate (PSS), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO)2)1, 2-Ethylene Glycol (EG), bismuth telluride (Bi)2Te3) Or one or more cresols. In other examples, the molar ratio of dispersant to dopant may be 1: 5 to 5: 1.
in some examples, the dispersed dopant may act as both a dispersant and a dopant in the aqueous dispersion. Additionally, in some examples, the dispersed dopant may be polystyrene sulfonate (PSS). This can enhance the water dispersibility of the conductive polymer and can increase the seebeck coefficient of the aqueous dispersion.
In some examples, the dispersed dopant can be sodium polystyrene sulfonate, potassium polystyrene sulfonate, or ammonium polystyrene sulfonate. In addition, examples of the present disclosure are not limited thereto, and for example, the dispersion dopant may be toluenesulfonic acid, β -naphthalenesulfonic acid, polystyrenesulfonic acid, or polyparastyrenesulfonic acid.
In some examples, the molecular weight of PSS may be in the range of 50000 to 1000000 Da. Thereby, the conductive polymer can be advantageously dispersed in water. For example, the molecular weight of PSS may be 50000Da, 100000Da, 200000Da, 300000Da, 400000Da, 500000Da, 600000Da, 700000Da, 800000Da, 900000Da or 1000000 Da.
The mechanism of action is described in detail below with P (AZ-co-EDOT) as the conductive polymer and PSS as the dispersed dopant, which can dissociate to give up one or more protons (H)+Ions) to protonate AZ, so that the AZ unit of P (AZ-co-EDOT) can be bound to PSS by ionic interaction, and P (AZ-co-EDOT) can be dispersed in water. This can improve the water dispersibility of the conductive polymer, and can contribute to the improvement of the seebeck coefficient. In addition, the ionic interaction of P (AZ-co-EDOT) with PSS in water results in a dramatic Seebeck effect. This makes it possible to provide an aqueous dispersion having a high seebeck coefficient.
In some examples, the molar mass ratio of conductive polymer to dispersed dopant can be from 1: 1 to 1: 4. Too much or too little dopant may cause instability or aggregation of the conductive polymer. This can facilitate the dispersion of the conductive polymer in water and the smooth progress of the polymerization reaction. For example, the molar mass ratio of conductive polymer to dispersed dopant can be 1: 1, 1: 2. 1: 3 or 1: 4.
In some examples, preferably, the molar mass ratio of conductive polymer to dispersed dopant may be 1: 1 to 1: 2. thereby, the conducting polymer can be further dispersed in water and better doped with the conducting polymer.
In some examples, the aqueous dispersion can have a conductivity of 0.05S/cm to 0.45S/cm. In other words, the adjustment range of the conductivity of the aqueous dispersion may be 0.05S/cm to 0.45S/cm.
In some examples, the aqueous dispersion may have a conductivity of 0.05S/cm, 0.1S/cm, 0.15S/cm, 0.2S/cm, 0.25S/cm, 0.3S/cm, 0.35S/cm, 0.4S/cm, or 0.45S/cm.
In some examples, the seebeck coefficient of the aqueous dispersion may be adjusted by adjusting the ratio of AZ monomer to EDOT monomer. In this case, the seebeck effect of the conductive polymer and the dispersed dopant can be changed by adjusting the ratio of the conductive polymer, and the seebeck coefficient of the aqueous dispersion can be adjusted.
In some examples, the aqueous dispersion may have a Seebeck coefficient of 1500 μ V/K to 2500 μ V/K. This can provide good thermoelectric efficiency. In other words, the adjustment range of the Seebeck coefficient of the aqueous dispersion may be 1500. mu.V/K to 2500. mu.V/K. For example, the aqueous dispersion may have a Seebeck coefficient of 1500. mu.V/K, 1600. mu.V/K, 1700. mu.V/K, 1800. mu.V/K, 1900. mu.V/K, 2000. mu.V/K, 2100. mu.V/K, 2200. mu.V/K, 2300. mu.V/K, 2400. mu.V/K or 2500. mu.V/K. This can enhance the thermoelectric efficiency of the aqueous dispersion.
In some examples, the thermoelectric efficiency of the aqueous dispersion can be characterized by a thermoelectric figure of merit (ZT value), ZT ═ S2σ T/κ, σ is the electrical conductivity, S is the Seebeck coefficient, κ is the thermal conductivity, and T is the absolute temperature. The ZT value and the power factor PF (PF ═ S)2σ) and thermal conductivity κ. In addition, the power factor can be increased by increasing the seebeck coefficient. For example, the power factor of the aqueous dispersion can be increased by increasing the seebeck coefficient of the aqueous dispersion, and the thermoelectric efficiency of the aqueous dispersion can be improved.
In some examples, the seebeck coefficient of a polymer film formed from the aqueous dispersion is about the same as the seebeck coefficient of the aqueous dispersion.
In some examples, the polymer film may have a light transmittance of greater than 90%. In this case, the polymer film can have good transparency, and thus can be applied to more scenes (e.g., transparent electrodes).
In the embodiment, the AZ monomer and the EDOT monomer can be polymerized to form a P (AZ-co-EDOT) conductive polymer having a stable electron donor-acceptor structure, the electrical conductivity of the aqueous dispersion can be adjusted by adjusting the ratio of the AZ monomer to the EDOT monomer, the water dispersibility of the P (AZ-co-EDOT) can be enhanced by the PSS, and the ionic interaction between the P (AZ-co-EDOT) and the PSS can form a huge seebeck effect, so that the aqueous dispersion has a high seebeck coefficient, and further the thermoelectric efficiency of the aqueous dispersion can be improved. Therefore, a polymer film formed from the aqueous dispersion can have a high seebeck coefficient.
Hereinafter, a method for producing an aqueous dispersion containing a conductive polymer (simply referred to as "production method") according to an example of the present embodiment will be described in detail with reference to fig. 2. Fig. 2 is a view showing a method for preparing an aqueous dispersion containing a conductive polymer according to an example of the present disclosure.
In some examples, the aqueous dispersion can be formed by in situ polymerization of reactive monomers (e.g., two reactive monomers) and a dispersing dopant in water.
In this embodiment, as shown in fig. 2, a method for preparing an aqueous dispersion containing a conductive polymer may include: mixing a reaction monomer, a dispersed dopant and water to obtain a mixed solution (step S100); adding an oxidant and a catalyst into the mixed solution, and carrying out in-situ polymerization to obtain a reaction solution with a dispersed phase (step S200); the inorganic salt in the reaction solution is removed, and then filtration is performed to obtain an aqueous dispersion containing a conductive polymer (step S300).
In some examples, in step S100, the reaction monomers may include Azulene (AZ) monomer and 3, 4-Ethylenedioxythiophene (EDOT) monomer.
In some examples, in step S100, the molar mass ratio of the AZ monomer and the EDOT monomer may be 10: 1 to 1: 10. in addition, the conductivity of the prepared aqueous dispersion can be adjusted by adjusting the ratio of AZ monomer to EDOT monomer. In addition, the dopant may be dispersed as described above.
In some examples, in step S100, the dispersion dopant may be polystyrene sulfonate (PSS).
In some examples, in step S100, the dispersion dopant may be a polystyrene sulfonate (PSS) solution. Thereby, the occurrence of subsequent in situ polymerization can be facilitated. In addition, the concentration of the PSS solution may be in the range of 15-25%. For example, the concentration of the PSS solution may be 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, or 25%. In some examples, in step S100, the concentration of the PSS solution may be preferably 20 to 25%.
In some examples, in step S100, the molecular weight of PSS may be in the range of 50000 to 1000000 Da. This can facilitate the progress of the subsequent polymerization reaction.
In some examples, in step S100, the PSS molecular weight may preferably be in the range of 800000 to 1000000 Da.
In some examples, the molar volume ratio of reaction monomer to water (mol: L) in step S100 can be from 1: 10 to 1: 30. Therefore, the conductive polymer can be favorably dispersed, and the subsequent polymerization reaction can be favorably carried out. For example, the molar volume ratio of reaction monomer to water (mol: L) can be 1: 10, 1: 15, 1: 20, 1: 25 or 1: 30. In addition, the molar mass of the reactive monomer may be the sum of the molar mass of the AZ monomer and the molar mass of the EDOT monomer.
In some examples, in step S100, the mixing may be performed at a temperature of 10 ℃ to 60 ℃. For example, the mixing can be carried out at 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃. Therefore, the mixed liquid which is uniformly mixed is favorably obtained.
In some examples, the order of addition of the reactive monomer, the dispersed dopant, and the water in step S100 is not particularly required.
In some examples, preferably, in step S100, the water and the dispersed dopant may be mixed and stirred for 1 hour and vacuum-pumped for 30 minutes.
In some examples, preferably, in step S100, nitrogen may be introduced before the reaction monomers are added. In this case, the introduction of nitrogen gas enables the removal of oxygen from the reaction environment. This can prevent the conductive polymer from being oxidized at high temperature.
In some examples, preferably, in step S100, after the reaction monomer, the dispersed dopant, and water are mixed, a uniformly mixed solution may be obtained by stirring, ultrasonic, oscillation, or the like. This can facilitate the progress of the subsequent polymerization reaction. For example, the mixing can be performed by manual stirring, ultrasonic stirring, magnetic stirring for 0.5 to 3 hours, and the like.
In some examples, in step S200, the reactive monomer may be polymerized by the action of a catalyst and an oxidant. In addition, in step S200, an in-situ polymerization reaction may occur.
In some examples, in step S200, the conductive polymer may be formed by polymerizing the reactive monomer. For example, AZ monomers and EDOT monomers may be polymerized to form P (AZ-co-EDOT).
In some examples, in step S200, the polymerization of AZ monomer and EDOT monomer may form a P (AZ-co-EDOT) conductive polymer having a stable electron donor-acceptor structure. This can enhance the stability of the aqueous dispersion. In some examples, P (AZ-co-EDOT) has a structure as shown in fig. 1, wherein n is an integer greater than zero and x is a number greater than zero and less than 1.
In some examples, the conductive polymer and the dispersed dopant may form a dispersed phase in step S200. In addition, the conductive polymer and the dispersed dopant may be combined by ionic interaction to form a dispersed phase.
In some examples, in step S200, the dispersed phase may be formed by the conductive polymer and the dispersed dopant being combined through ionic interaction.
In some examples, in step S200, an in-situ polymerization reaction may occur after the oxidant and the catalyst are added to the mixed solution to obtain a reaction solution having a dispersed phase.
In some examples, the molar mass ratio of the conductive polymer to the dispersed dopant in step S200 may be 1: 1 to 1: 4. Thereby, the dispersion of the conductive polymer can be facilitated, and the progress of the polymerization reaction can be facilitated. For example, the molar mass ratio of conductive polymer to dispersed dopant can be 1: 1, 1: 2. 1: 3 or 1: 4.
In some examples, in step S200, the oxidizing agent may be at least one selected from the group consisting of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, and silver perchlorate. Thereby, the polymerization reaction is facilitated. In addition, examples of the present disclosure are not limited thereto, and for example, the oxidizing agent may be peroxodisulfuric acid, iron p-toluenesulfonate.
In some examples, the molar mass ratio of reaction monomer to oxidant in step S200 can be 1: 1 to 1: 5. This can facilitate the progress of the polymerization reaction. For example, the molar mass ratio of reactant monomer to oxidant can be 1: 1, 1: 2. 1: 3. 1: 4 or 1: 5.
In some examples, in step S200, the catalyst may be ferrous sulfate or ferric chloride. In this case, the catalyst can increase the reaction rate of the polymerization reaction, and thus can facilitate the progress of the polymerization reaction. In addition, examples of the present disclosure are not limited thereto, and for example, the catalyst may be aluminum trichloride or tin tetrachloride.
In some examples, in step S200, the catalyst may be potassium persulfate and ferric chloride.
In some examples, the molar mass ratio of reaction monomer to catalyst in step S200 may be from 1: 0.005 to 1: 0.015. This reduces the occurrence of peroxidation and unnecessary polymerization crosslinking reaction, and facilitates the progress of the polymerization reaction. For example, the molar mass ratio of reaction monomer to catalyst can be 1: 0.005, 1:0.01 or 1: 0.015.
In some examples, the order of addition of the oxidant and the catalyst in step S200 is not particularly required. For example, the oxidizing agent may be added first, followed by the catalyst.
In some examples, in step S200, after the oxidant and the catalyst are added to the mixed solution, a reaction solution with uniform mixing and sufficient reaction can be obtained by stirring, ultrasonic, oscillation, and the like. For example, it may be stirred for 4 to 24 hours to sufficiently mix and react to obtain a reaction liquid.
In some examples, preferably, in step S200, stirring may be performed under a constant temperature condition of 60 ℃ after the oxidant and the catalyst are added to the mixed solution. This makes it possible to obtain a reaction solution which is uniformly mixed and sufficiently reacted.
In some examples, in step S200, inorganic salts and impurities may be included in the reaction liquid. In some examples, the inorganic salts may include oxidizing agents, catalysts, and other salt species that may be present. In addition, inorganic salts may have an adverse effect on the seebeck coefficient and the electrical conductivity. Therefore, it is necessary to remove the inorganic salt in the reaction solution.
In some examples, in step S300, the inorganic salts may be removed by filtration purification using an anion and cation exchange resin. In addition, the anion and cation exchange resins can be weakly basic anion exchange resins and weakly acidic cation exchange resins. This enables the removal of inorganic salts in the reaction solution.
In some examples, in step S300, filtration may be performed using an ultrafiltration membrane. This can remove impurities in the reaction solution. The ultrafiltration membrane may be a polyvinylidene fluoride membrane.
In some examples, in step S300, impurities in the reaction liquid may be removed by centrifugal filtration. For example, the reaction solution may be centrifugally filtered at 5000 to 15000rpm to remove impurities.
In this embodiment, specific description about the aqueous dispersion containing a conductive polymer prepared by the preparation method can be referred to the above description of the aqueous dispersion.
In the present embodiment, a P (AZ-co-EDOT) conductive polymer having a stable electron donor-acceptor structure is formed by polymerizing an AZ monomer and an EDOT monomer, and the electrical conductivity of an aqueous dispersion can be adjusted by adjusting the ratio of the AZ monomer to the EDOT monomer, PSS is used as a dispersion dopant to enhance the water dispersibility of P (AZ-co-EDOT), and the ionic interaction between P (AZ-co-EDOT) and PSS can form a huge seebeck effect, whereby an aqueous dispersion having a high seebeck coefficient can be obtained.
According to the present disclosure, it is possible to provide an aqueous dispersion containing a conductive polymer having a high seebeck coefficient and adjustable conductivity and a method for preparing the same.
To further illustrate the present disclosure, the aqueous dispersion containing a conductive polymer provided by the present disclosure is described in detail below with reference to examples, and the advantageous effects achieved by the present disclosure are fully illustrated with reference to comparative examples.
In the examples and comparative examples of the present disclosure, the reaction monomers were Azulene (AZ) monomer (99% purity) and 3, 4-Ethylenedioxythiophene (EDOT) monomer (99% purity), the dispersing dopant was sodium polystyrene sulfonate solution (concentration 25%) having a molecular weight of 1000000Da, the oxidizing agent was potassium persulfate monomer, and the catalyst was iron chloride monomer.
[ examples ]
First, the raw materials of each example (example 1 to example 5) were prepared according to table 1, respectively, 20ml of water was weighed into a 2-necked round-bottomed flask at room temperature, 2ml of sodium polystyrenesulfonate solution was poured into the above solution, stirred for 1 hour at 800rpm using a magnetic stirrer, and evacuated for 30 minutes; then adding the reaction monomer into the flask under the atmosphere of nitrogen, and continuing stirring for 2 hours; then, 110mg of oxidant and 10mg of catalyst are respectively added, and the mixture is stirred for 24 hours at a constant temperature of 60 ℃ to obtain a blue-black solution; appropriate amounts of anion exchange resin and cation exchange resin were added to perform exchange reaction for 2 hours, respectively, and filtered through a PVDF membrane to obtain the aqueous dispersions containing the conductive polymers of examples 1 to 5.
Then, the aqueous dispersions obtained in the respective examples were dropped onto a glass substrate and air-dried for 3 hours to prepare polymer films.
Next, the polymer film obtained from the aqueous dispersion obtained in each example was examined. The specific detection items are as follows:
(1) light transmittance: the visible light transmittance of the polymer films prepared in the respective examples was measured, and the results are shown in table 2.
(2) Conductivity: the conductivity of the polymer films prepared in the respective examples was measured, and the results are shown in table 2.
(3) Seebeck coefficient: the seebeck coefficient of each polymer film produced in each example was measured, and the results are shown in table 2.
TABLE 1
Comparative example 1
Weighing 20ml of water into a 2-neck round-bottom flask at room temperature, pouring 2ml of sodium polystyrene sulfonate solution into the solution, stirring for 1 hour at the rotating speed of 800rpm by using a magnetic stirrer, and vacuumizing for 30 minutes; 109mg of 3, 4-ethylenedioxythiophene were then added to the flask under a nitrogen atmosphere and stirring was continued for 2 hours; then, 110mg of oxidant and 10mg of catalyst are respectively added, and the mixture is stirred for 24 hours at a constant temperature of 60 ℃ to obtain a dark blue solution; appropriate amounts of anion exchange resin and cation exchange resin were added to perform exchange reaction for 2 hours, respectively, and filtered through a PVDF membrane to obtain the aqueous dispersion containing the conductive polymer of comparative example 1.
Then, the aqueous dispersion obtained in comparative example 1 was dropped onto a glass substrate and air-dried for 3 hours to prepare a polymer film.
Then, the polymer film obtained from the aqueous dispersion obtained in comparative example 1 was tested, and the test items were the same as those of the examples, and the test results are shown in Table 2.
Table 2 data for polymer films
As can be seen from table 2, the conductivity of the polymer films in the examples was also different in the case of different ratios of AZ monomer to EDOT monomer, and thus it was found that the conductivity of the polymer films in the examples can be adjusted by adjusting the ratio of AZ monomer to EDOT monomer, that is, the conductivity of the aqueous dispersions in the examples can be adjusted by adjusting the ratio of AZ monomer to EDOT monomer.
As can be seen from Table 2, the Seebeck coefficient of the polymer film in the example was 1500-2500. mu.V/K, and that of the polymer film in the comparative example was 210. mu.V/K, and it can be seen that the Seebeck coefficient of the polymer film in the example was significantly improved as compared with that of the polymer film in the comparative example, that is, the polymer film in the example had a higher Seebeck coefficient, that is, the aqueous dispersion in the example had a higher Seebeck coefficient.
As can be seen from table 2, the polymer films in the examples had a visible light transmittance of 93% to 96%, and thus it can be seen that the polymer films in the examples had good transparency.
Claims (10)
1. An aqueous dispersion comprising an electrically conductive polymer, comprising water and a dispersed phase dispersed in the water, the dispersed phase being formed by ionic interaction of the electrically conductive polymer with a dispersed dopant in a molar mass ratio of from 1: 1 to 1: 4, the electrically conductive polymer being P (AZ-co-EDOT), the dispersed dopant being polystyrene sulfonate (PSS), the P (AZ-co-EDOT) having the formula:
wherein n is an integer greater than zero, x is a number greater than zero and less than 1; and is
The disperse phase is formed by in-situ polymerization of an Azulene (AZ) monomer, a 3, 4-Ethylenedioxythiophene (EDOT) monomer and a disperse doping agent, the conductivity of the aqueous dispersion is adjustable, and the conductivity of the aqueous dispersion is adjusted by adjusting the ratio of the AZ monomer to the EDOT monomer.
2. The aqueous dispersion of claim 1, wherein:
the particle size of the dispersed phase is 0.5 to 2 μm.
3. The aqueous dispersion of claim 1, wherein:
the molar mass ratio of the AZ monomer to the EDOT monomer is 10: 1 to 1: 10.
4. the aqueous dispersion according to claim 1 or 3, characterized in that:
the conductivity of the aqueous dispersion is 0.05S/cm to 0.45S/cm.
5. The aqueous dispersion of claim 1, wherein:
the aqueous dispersion has a Seebeck coefficient of 1500 to 2500 [ mu ] V/K.
6. A process for producing an aqueous dispersion containing a conductive polymer,
the method comprises the following steps:
1) mixing a reaction monomer, a dispersing dopant and water to obtain a mixed solution, wherein the reaction monomer is an Azulene (AZ) monomer and a 3, 4-Ethylenedioxythiophene (EDOT) monomer, and the molar mass ratio of the AZ monomer to the EDOT monomer is 10: 1 to 1: 10, the dispersed dopant is polystyrene sulfonate (PSS);
2) adding an oxidant and a catalyst to the mixed solution, and carrying out in-situ polymerization to obtain a reaction solution having a dispersed phase formed by combining a conductive polymer and a dispersed dopant through ionic interaction, wherein the molar mass ratio of the conductive polymer to the dispersed dopant is 1: 1 to 1: 4; and is
3) Removing inorganic salts in the reaction liquid, and filtering to obtain an aqueous dispersion containing a conductive polymer, wherein the conductivity of the aqueous dispersion is adjusted by adjusting the ratio of the AZ monomer to the EDOT monomer, the conductive polymer is P (AZ-co-EDOT), and the structural formula of the P (AZ-co-EDOT) is as follows:
where n is an integer greater than zero and x is a number greater than zero and less than 1.
7. The method of claim 6, wherein the step of preparing the composition comprises
The oxidant is at least one selected from potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide and silver perchlorate, and the molar mass ratio of the reaction monomer to the oxidant is 1: 1-1: 5.
8. The method of claim 6, wherein the step of preparing the composition comprises
The catalyst is ferrous sulfate or ferric chloride, and the molar mass ratio of the reaction monomer to the catalyst is 1: 0.005 to 1: 0.015.
9. The method of claim 6, wherein the step of preparing the composition comprises
The molar volume ratio of the reaction monomer to the water (mol: L) is from 1: 10 to 1: 30.
10. The method of claim 6, wherein the step of preparing the composition comprises
In the step 3), the inorganic salt is removed by utilizing anion and cation exchange resin, and the ultrafiltration membrane is used for filtering, wherein the ultrafiltration membrane is a polyvinylidene fluoride membrane.
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