CN101824207A - Conductive polymer aqueous dispersion liquid, preparation method and application thereof - Google Patents

Abstract

The conductive polymer aqueous dispersion liquid of the invention consists of distilled water, a dispersed phase A dispersed in the distilled water and a post-treatment agent B; the weight proportion of the distilled water, the dispersed phase A and the post-treatment agent B is 69-20: 30-70: 1-10; the molar ratio of the conductive polymer monomer, the oxidant and the dopant in the dispersed phase A is 1: 2-7.5: 10-20; the preparation method comprises the following steps: adding the dispersion phase A into distilled water at the temperature of between 20 ℃ below zero and 50 ℃, and reacting for 12 to 48 hours under stirring; then stopping stirring and reacting, standing, and pouring out supernatant liquor; adding a post-treatment agent into the system, continuously reacting under stirring, and filtering to obtain a conductive polymer aqueous dispersion liquid after the reaction is completed; the conductive polymer aqueous dispersion has the characteristics of high conductivity, good transparency and good heat resistance after film formation, and the operation process is very simple and easy for industrial production.

Description

Conductive polymer aqueous dispersion and its preparation method and use

technical field

The invention relates to a conductive polymer aqueous dispersion liquid and its preparation method and application.

Background technique

Conductive polymers have become a research hotspot in the field of functional materials in recent years. Conductive polymers have the characteristics of reversible and adjustable conductivity in a wide range (10 ^-9 ~ 10 ⁵ S/cm), controllable molecular structure, and easy multi-functionalization. They are used in organic electroluminescent devices, electrochromic devices, and electronic paper. High-tech fields such as plastic memory, solar cells, electrolytic capacitors and sensors have attractive application prospects; at the same time, they are also widely used in anti-static materials, electromagnetic shielding, wave-absorbing materials, anti-corrosion materials and conductive fibers. However, the insolubility of conductive polymers in many common solvents is one of the key factors affecting their application and development. Therefore, obtaining soluble conductive polymers is an important problem that needs to be solved urgently in this field.

At present, soluble conductive polymers can be prepared by various methods such as structural modification (substitution, grafting or copolymerization), emulsion polymerization or functional doping. Among them, functional doping is to use soluble dopants to obtain soluble conductive polymers. This method is effective, cheap and simple, and is suitable for large-scale preparation. Polystyrene sulfonic acid and its water-soluble salts are low toxicity and good water-soluble emulsifiers. When used as a dopant for conductive polymers, aqueous dispersions of conductive polymers can be prepared. For example, poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid aqueous dispersion (PEDOT/PSS for short) has been the first commercial product launched by German Bayer company, but its conductivity is low at present, the highest is only To 1S/cm, seriously affecting its application.

Contents of the invention

The purpose of the present invention is to provide a high-conductivity conductive polymer aqueous dispersion and a preparation method thereof. The conductive polymer aqueous dispersion obtained by the method has high conductivity after film formation, and good transparency and heat resistance. The method is simple and effective, has low cost and is easy for industrialized production.

Another object of the present invention is that the conductive polymer aqueous dispersion obtained by the present invention can be used for electrode materials, electroluminescent or electrochromic materials, antistatic materials, electromagnetic shielding, wave-absorbing materials, anti-corrosion materials and Preparation of conductive fibers.

Technical scheme of the present invention is as follows:

The conductive polymer aqueous dispersion provided by the present invention is composed of distilled water, dispersed phase A and post-treatment agent B dispersed in the distilled water;

The weight ratio of the distilled water to the dispersed phase A and the post-treatment agent B=69-20:30-70:1-10;

The dispersed phase A is a polymer produced by the polymerization reaction of the conductive polymer monomer, the oxidant and the dopant; the molar ratio of the conductive polymer monomer, the oxidant and the dopant in the dispersed phase A is 1 :2-7.5:10-20;

The conductive polymer monomer is poly-3,4-ethylenedioxythiophene, aniline monomer or pyrrole monomer;

The oxidant is sodium persulfate, ammonium persulfate or ferric chloride; or a mixture of sodium persulfate and ferric chloride; or a mixture of ammonium persulfate and ferric sulfate;

The dopant is poly(p-styrenesulfonic acid) or a water-soluble salt of poly(p-styrenesulfonic acid);

The post-treatment agent is tetrafluoroboric acid-1-ethyl-3-methylimidazole, sodium p-toluenesulfonate, iron p-toluenesulfonate, 1-ethyl-3-methylimidazole hydroiodide, p-toluene Sulfonic acid or 1-ethyl-3-methylimidazolium triflate.

The preparation method of conductive polymer aqueous dispersion liquid provided by the invention, its steps are as follows:

1) Add the dispersed phase A into distilled water at -20°C to 50°C, and react for 12h-48h under stirring; then stop the stirring reaction, let stand, and pour out the supernatant;

The dispersed phase A is a polymer produced by the polymerization reaction of the conductive polymer monomer, the oxidant and the dopant; the molar ratio of the conductive polymer monomer, the oxidant and the dopant in the dispersed phase A is 1 ;2-7.5:10-20;

The conductive polymer monomer is 3,4-ethylenedioxythiophene, aniline monomer or pyrrole monomer;

The oxidant is sodium persulfate, ammonium persulfate or ferric chloride; or a mixture of sodium persulfate and ferric chloride; or a mixture of ammonium persulfate and ferric sulfate;

The dopant is poly(p-styrenesulfonic acid) or a water-soluble salt of poly(p-styrenesulfonic acid);

2) Add post-processing agent to the system, continue to react under stirring, after the reaction is complete, filter to obtain a high-conductivity conductive polymer aqueous dispersion;

The weight ratio of the distilled water to the dispersed phase A and the post-treatment agent B is 69-20:30-70:1-10.

The use of the conductive polymer aqueous dispersion provided by the present invention can be used to prepare a conductive film by spin spraying or coating.

The use of the conductive polymer aqueous dispersion liquid provided by the invention can be mixed with a polymer material solution and used as an additive of a conductive material.

The use of the conductive polymer aqueous dispersion provided by the present invention, which can be used to prepare electronic device materials, electroluminescent materials, electrochromic materials, antistatic materials, electromagnetic shielding materials, wave-absorbing materials, anti-corrosion materials or conductive fiber materials .

Compared with the prior art, the present invention has the advantages of:

1. The conductive polymer aqueous dispersion provided by the present invention greatly improves the conductivity after film formation through simple post-treatment, and has excellent film-forming performance;

2. The conductivity of the conductive polymer aqueous dispersion provided by the present invention can be adjusted by controlling the ratio of dopant, oxidizing agent and monomer in the reaction, and adjusting the polymerization temperature and other conditions to adjust the conductivity of the material after film formation. To meet the needs of different technical applications;

3. The chemical oxidation preparation method provided by the present invention is simple and easy to implement, has simple equipment, and is suitable for large-scale production.

4. The conductive polymer aqueous dispersion provided by the present invention can be made into a conductive film by processing methods such as spin spraying, and can also be mixed with a variety of polymer material solutions, and can also be used as an additive, and in electronic devices, electroluminescence, etc. Or electrochromic materials, anti-static materials, electromagnetic shielding, wave-absorbing materials, anti-corrosion materials, conductive fibers, etc. have been widely used.

Description of drawings

Figure 1 is the ultraviolet spectrum of the PEDOT/PSS films with different thicknesses prepared in Example 1; the film thicknesses of a, b, c, and d in the figure are 0.1 μm, 0.5 μm, 1 μm, and 2 μm, respectively.

Figure 2 is the UV spectrum of the PANI/PSS films with different thicknesses prepared in Example 6; the film thicknesses of a, b, and c in the figure are 0.5 μm, 1 μm, and 2 μm, respectively.

Fig. 3 is the ultraviolet spectrogram of the PPy/PSS film with a thickness of 0.5 μm prepared in Example 11.

Fig. 4 is the thermal weight loss curve of the powder material obtained by grinding the PEDOT/PSS, PANI/PSS and PPy/PSS prepared in Examples 1, 6, and 11 after drying into a film.

Detailed ways

Embodiment 1, preparation high conductivity PEDOT/PSS aqueous dispersion liquid of the present invention

At 0°C, add 0.5mL of EDOT monomer;

3.2g ammonium persulfate + 2.8g ferric sulfate (oxidizing agent); and

9.6g sodium polystyrene sulfonate (dopant) was sequentially added to 20mL distilled water, and reacted for 24 hours while stirring; after that, the stirring and reaction were stopped, left standing for 48 hours, and the supernatant liquid was poured out;

The mol ratio of described EDOT monomer and ammonium persulfate, ferric sulfate and polysodium p-styrene sulfonate is 1: 3: 1.5: 10;

Then add 0.5g tetrafluoroboric acid-1-ethyl-3-methylimidazole (post-treatment agent) in the system, continue to stir and react after 4h, filter, obtain the high conductivity PEDOT/PSS aqueous dispersion liquid of the present embodiment ( dark blue) 28g. In this aqueous dispersion, tetrafluoroboric acid-1-ethyl-3-methylimidazole accounts for 1.8% (ie: 0.5÷28=0.018), and PEDOT/PSS accounts for 36.2% (the calculation method of this value is: 1g aqueous dispersion After the liquid is dried, 0.38 g of solid product is obtained, and the weight percentage of PEDOT/PSS is: 0.38-0.018=0.362), and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PEDOT/PSS. The ultraviolet spectra of films of different thicknesses prepared using this product are shown in Figure 1. It can be seen that it has good light transmission in the visible region; the TG curve provided in Figure 4 shows that it has good heat resistance; The room temperature conductivity of the film was determined to be 380 S/cm by four-probe electrode method. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent light sky blue to dark blue in the range of -0.5 ~ +1.5V.

Embodiment 2, preparation high conductivity PEDOT/PSS aqueous dispersion liquid of the present invention

At 0°C, add 0.5mL of EDOT monomer;

3.2g ammonium persulfate + 2.8g ferric sulfate (oxidizing agent); and

19.2g sodium polystyrene sulfonate (dopant) was sequentially added to 20mL distilled water, and reacted for 12 hours while stirring; after that, the stirring and reaction were stopped, left standing for 48 hours, and the supernatant liquid was poured out;

The mol ratio of described EDOT monomer to ammonium persulfate, ferric sulfate and polysodium p-styrene sulfonate is 1: 3: 1.5: 20;

Then add 0.5g tetrafluoroboric acid-1-ethyl-3-methylimidazole to the system, continue to stir and react for 4h, then filter to obtain 35.4g of the high conductivity PEDOT/PSS aqueous dispersion (dark blue) of this embodiment . In this aqueous dispersion, tetrafluoroboric acid-1-ethyl-3-methylimidazole accounted for 1.4%, PEDOT/PSS accounted for 56.2%, and the rest was water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PEDOT/PSS. The room temperature conductivity of the film was determined by four-probe electrode method to be 105S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent light sky blue to dark blue in the range of -0.5 ~ +1.5V.

Embodiment 3, preparation high conductivity PEDOT/PSS aqueous dispersion liquid of the present invention

At 20°C, add 0.5mL of EDOT monomer;

2.8g ammonium persulfate + 1.9g ferric sulfate (oxidizing agent); and

9.6g sodium polystyrene sulfonate (dopant) was sequentially added to 20mL distilled water, and reacted for 24 hours while stirring; after that, the stirring and reaction were stopped, left standing for 48 hours, and the supernatant liquid was poured out;

The mol ratio of described EDOT monomer and ammonium persulfate, ferric sulfate and polysodium p-styrene sulfonate is 1: 2.53: 2.5: 10;

Then add 0.5g tetrafluoroboric acid-1-ethyl-3-methylimidazole to the system, continue to stir and react for 4h, then filter to obtain 27.1g of the high conductivity PEDOT/PSS aqueous dispersion (dark blue) of this embodiment . In this aqueous dispersion, tetrafluoroboric acid-1-ethyl-3-methylimidazole accounts for 1.85%, PEDOT/PSS accounts for 37.9%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PEDOT/PSS. The room temperature conductivity of the film was determined to be 212 S/cm by four-probe electrode method. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent light sky blue to dark blue in the range of -0.5 ~ +1.5V.

Embodiment 4, preparation high conductivity PEDOT/PSS aqueous dispersion liquid of the present invention

At 50°C, 0.5mL of EDOT monomer, 2.8g of sodium persulfate, 1.9g of ferric chloride (oxidant) and 9.6g of polystyrene sodium sulfonate (dopant) were sequentially added to 20mL of distilled water to react After 14h, stop stirring, then stand still for 48h, pour out the supernatant; The molar ratio of described EDOT monomer and ammonium persulfate, iron sulfate and polysodium p-styrene sulfonate is 1: 2.5: 2.5: 10;

Add 1.5 g of sodium p-toluenesulfonate to the system, continue to stir and react for 4 hours, and then filter to obtain 28.1 g of the high-conductivity PEDOT/PSS aqueous dispersion (dark blue) of this example. In this aqueous dispersion, sodium p-toluenesulfonate accounts for 5.3%, PEDOT/PSS accounts for 36.6%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PEDOT/PSS. The room temperature conductivity of the film was determined to be 180 S/cm by four-probe electrode method. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent light sky blue to dark blue in the range of -0.5 ~ +1.5V.

Embodiment 5, preparation high conductivity PEDOT/PSS aqueous dispersion liquid of the present invention

At -20°C, 0.5mL of EDOT monomer, 5.6g of sodium persulfate (oxidant) and 14.4g of polystyrene sodium sulfonate (dopant) were sequentially added to 20mL of distilled water, and after 24 hours of reaction, the stirring was stopped. Then stand still for 48h, pour out the supernatant liquid; the mol ratio of described EDOT monomer and ammonium persulfate, ferric sulfate and polystyrene sodium sulfonate is 1: 5: 15; Add 2.5g p-toluene in the system again Iron sulfonate, after continuing to stir and react for 4h, filtered to obtain 33.4g of the high-conductivity PEDOT/PSS aqueous dispersion (dark blue) of the present embodiment. In this aqueous dispersion, iron p-toluenesulfonate accounts for 7.5%, PEDOT/PSS accounts for 45.1%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PEDOT/PSS. The room temperature conductivity of the film was determined by four-probe electrode method to be 265 S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent yellow-green to dark grass green in the range of -0.5 ~ +1.5V.

Embodiment 6, preparation high conductivity PANI/PSS aqueous dispersion liquid of the present invention

At -20°C, add 0.43mL of aniline monomer, 5.4g of ammonium persulfate (oxidant) and 9.6g of sodium polystyrene sulfonate (dopant) into 20mL of distilled water in sequence, and after reacting for 24 hours, stop stirring. Stand still for 48 hours, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1:5:10; then add 0.5g of 1-ethyl-3-methylimidazole hydrogen iodide to the system acid salt, after continuing to stir and react for 4h, filter to obtain the high conductivity PANI/PSS aqueous dispersion (dark green) 27.5g of the present embodiment. In this aqueous dispersion, 1-ethyl-3-methylimidazolium hydroiodide accounts for 1.8%, PANI/PSS accounts for 36.9%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PANI/PSS. The ultraviolet spectrum of the film with different thicknesses of the product is shown in Figure 2, it can be seen that it has good light transmittance in the visible light region. The TG curve given in Figure 4 shows that its heat resistance is good. The room temperature conductivity of the film was determined by the four-probe electrode method to be 0.22 S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent yellow-green to dark grass green in the range of -0.4 ~ +1.0V.

Embodiment 7, preparation high conductivity PANI/PSS aqueous dispersion liquid of the present invention

At 0°C, add 0.43mL of aniline monomer, 2.7g of ammonium persulfate (oxidant) and 19.2g of polystyrene sodium sulfonate (dopant) into 20mL of distilled water in sequence, and after reacting for 12 hours, stop stirring and let Stand for 48h, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1: 2.5: 20;

Then add 2g of tetrafluoroborate-1-butyl-3-methylimidazole to the system, continue to stir and react for 4h, then filter to obtain 34.3g of the high conductivity PANI/PSS aqueous dispersion (dark green) of this example. In this aqueous dispersion, 1-butyl-3-methylimidazole tetrafluoroborate accounted for 5.8%, PANI/PSS accounted for 57.8%, and the rest was water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PANI/PSS. The room temperature conductivity of the film was determined by four-probe electrode method to be 0.083S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent yellow-green to dark grass green in the range of -0.4 ~ +1.0V.

Embodiment 8, preparation high conductivity PANI/PSS aqueous dispersion liquid of the present invention

At 10°C, add 0.43mL of aniline monomer, 5.6g of sodium persulfate (oxidant) and 9.6g of polystyrene sulfonate (dopant) into 20mL of distilled water in sequence. After 12 hours of reaction, stop stirring and let the Set aside for 48 hours, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1:5:10; then add 1.5g p-toluenesulfonic acid to the system, continue to stir and react for 4 hours, and filter , Obtain 28.7g of the high conductivity PANI/PSS aqueous dispersion (dark green) of the present embodiment. In this aqueous dispersion, p-toluenesulfonic acid accounts for 5.2%, PANI/PSS accounts for 35.5%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PANI/PSS. The room temperature conductivity of the film was determined by the four-probe electrode method to be 0.11 S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent yellow-green to dark grass green in the range of -0.4 ~ +1.0V.

Embodiment 9, preparation of high conductivity PANI/PSS aqueous dispersion liquid of the present invention

At 20°C, add 0.43mL of aniline monomer, 5.7g of ferric chloride (oxidant) and 9.6g of polystyrene sodium sulfonate (dopant) into 20mL of distilled water in sequence, and after reacting for 12 hours, stop stirring. Stand still for 48h, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1:7.5:10; then add 2g of iron p-toluenesulfonate to the system, and continue to stir and react for 4h, Filter to obtain the high conductivity PANI/PSS aqueous dispersion (dark green) of the present embodiment, 29.3g. In this aqueous dispersion, iron p-toluenesulfonate accounts for 6.8%, PANI/PSS accounts for 34.8%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PANI/PSS. The room temperature conductivity of the film was determined by the four-probe electrode method to be 0.15 S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent yellow-green to dark grass green in the range of -0.4 ~ +1.0V.

Embodiment 10, preparation of high conductivity PANI/PSS aqueous dispersion liquid of the present invention

At 50°C, add 0.43mL of aniline monomer, 5.7g of ferric chloride (oxidant) and 19.2g of polystyrene sodium sulfonate (dopant) into 20mL of distilled water in sequence, and after reacting for 12 hours, stop stirring. Let it stand for 48 hours, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidant and the dopant is 1:7.5:20; then add 2g of 1-ethyl-3-methylimidazole trifluoro Methanesulfonate, continue to stir and react for 4h, then filter to obtain 36.6g of the high conductivity PANI/PSS aqueous dispersion (dark green) of this embodiment. In this aqueous dispersion, 1-ethyl-3-methylimidazole trifluoromethanesulfonate accounted for 36.6%, PANI/PSS accounted for 54.1%, and the rest was water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PANI/PSS. The room temperature conductivity of the film was determined by four-probe electrode method to be 0.072S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent yellow-green to dark grass green in the range of -0.4 ~ +1.0V.

Embodiment 11, preparation of high conductivity PPy/PSS aqueous dispersion liquid of the present invention

At -20°C, add 0.33mL of pyrrole monomer, 3.0g of ferric chloride (oxidant) and 9.6g of sodium poly(p-styrene sulfonate) (dopant) to 20mL of distilled water in sequence, after 12 hours of reaction, stop stirring , let stand for 48h, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1:4:10; then add 2g of 1-ethyl-3-methylimidazole three Fluoromethylsulfonate, after continuing to stir and react for 4 hours, filtered to obtain 27.3 g of the high conductivity PPy/PSS aqueous dispersion (purple black) of this embodiment. In this aqueous dispersion, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate accounted for 7.3%, PPy/PSS accounted for 37.6%, and the rest was water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PPy/PSS. The ultraviolet spectrum of the PPy/PSS film with a thickness of 0.5 μm is shown in Figure 3, and it can be seen that it has good light transmittance in the visible region. The TG curve given in Figure 4 shows that its heat resistance is good. The room temperature conductivity of the film was determined to be 15 S/cm by four-probe electrode method. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent yellow-green to dark grass green in the range of -0.4 ~ +1.0V.

Embodiment 12, preparation of high conductivity PPy/PSS aqueous dispersion of the present invention

At 0°C, add 0.33 mL of pyrrole monomer, 4.5 g of ferric chloride (oxidant) and 9.6 g of sodium polystyrene sulfonate (dopant) to 20 mL of distilled water in sequence, and after reacting for 12 hours, stop stirring. Let it stand for 48 hours, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidant and the dopant is 1:6:10; then add 2g of 1-ethyl-3-methylimidazole trifluoro Methanesulfonate, continue to stir and react for 4h, then filter to obtain 28.4g of the high conductivity PPy/PSS aqueous dispersion (purple black) of this embodiment. In this aqueous dispersion, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate accounts for 7.0%, PPy/PSS accounts for 36.0%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PPy/PSS. The room temperature conductivity of the film was determined by four-probe electrode method to be 8.8 S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent lavender to purple black in the range of -0.5 ~ +1.5V.

Embodiment 13, preparation of high conductivity PPy/PSS aqueous dispersion liquid of the present invention

At 20°C, add 0.33mL of pyrrole monomer, 1.5g of ferric chloride (oxidant) and 19.2g of polystyrene sodium sulfonate (dopant) into 20mL of distilled water in sequence, and after reacting for 12h, stop stirring. Stand still for 48h, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1:2:20; add 1.5g 1-ethyl-3-methylimidazolium hydrogen to the system After continuing to stir for 4 hours, filter the iodate to obtain 33.0 g of the high conductivity PPy/PSS aqueous dispersion (purple black) of this embodiment. In the aqueous dispersion, 1-ethyl-3-methylimidazolium hydroiodide accounts for 4.5%, PPy/PSS accounts for 60.1%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PPy/PSS. The room temperature conductivity of the film was determined to be 6.3 S/cm by four-probe electrode method. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent lavender to purple black in the range of -0.5 ~ +1.5V.

Embodiment 14, preparation of high conductivity PPy/PSS aqueous dispersion liquid of the present invention

At 50°C, add 0.33mL of pyrrole monomer, 1.5g of ferric chloride (oxidant) and 9.6g of polystyrene sodium sulfonate (dopant) into 20mL of distilled water in sequence, after reacting for 12h, stop stirring, Stand still for 48h, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1:2:10; then add 1.5g 1-ethyl-3-methylimidazolium hydrogen to the system After iodate was stirred and reacted for 4h, it was filtered to obtain a purple-black aqueous dispersion product, 25.6g. In this aqueous dispersion, 1-ethyl-3-methylimidazolium hydroiodide accounts for 5.9%, PPy/PSS accounts for 40.0%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PPy/PSS. The room temperature conductivity of the film was determined to be 12 S/cm by four-probe electrode method. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent lavender to purple black in the range of -0.5 ~ +1.5V.

Embodiment 15, preparation of high conductivity PPy/PSS aqueous dispersion liquid of the present invention

At 20°C, add 0.33mL of pyrrole monomer, 1.5g of ferric chloride (oxidant) and 9.6g of polystyrene sodium sulfonate (dopant) into 20mL of distilled water in sequence, after reacting for 12h, stop stirring, Stand still for 48h, then pour out the supernatant; the molar ratio of the aniline monomer to the oxidizing agent and the dopant is 1:2:10; then add 1.5g 1-ethyl-3-methylimidazolium hydrogen to the system The iodate was stirred and reacted for 4 hours, and filtered to obtain 25.6 g of a purple-black aqueous dispersion product. In this aqueous dispersion, 1-ethyl-3-methylimidazolium hydroiodide accounts for 5.9%, PPy/PSS accounts for 40.0%, and the rest is water.

The results of infrared and ultraviolet spectra prove that it is a typical structure of PPy/PSS. The room temperature conductivity of the film was determined by four-probe electrode method to be 4.8 S/cm. After it was formed into a film on ITO glass by spin coating, as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and a _platinum electrode was used as a counter electrode. Electrochromic performance, found that it can change from transparent lavender to purple black in the range of -0.5 ~ +1.5V.

Claims (5)

1. an aqueous dispersion of conductive polymer, it is characterized in that, it is made up of distilled water, dispersed phase A and post-treatment agent B dispersed in described distilled water; The weight ratio of the distilled water to the dispersed phase A and the post-treatment agent B=69-20:30-70:1-10; The dispersed phase A is a polymer produced by the polymerization reaction of the conductive polymer monomer, the oxidant and the dopant; the molar ratio of the conductive polymer monomer, the oxidant and the dopant in the dispersed phase A is 1 :2-7.5:10-20; The conductive polymer monomer is poly-3,4-ethylenedioxythiophene, aniline monomer or pyrrole monomer; The oxidant is sodium persulfate, ammonium persulfate or ferric chloride; or a mixture of sodium persulfate and ferric chloride; or a mixture of ammonium persulfate and ferric sulfate; The dopant is poly(p-styrenesulfonic acid) or a water-soluble salt of poly(p-styrenesulfonic acid); The post-treatment agent is tetrafluoroboric acid-1-ethyl-3-methylimidazole, sodium p-toluenesulfonate, iron p-toluenesulfonate, 1- Ethyl-3-methylimidazolium hydroiodide, p-toluenesulfonic acid or 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. 2. a preparation method of the conductive polymer aqueous dispersion according to claim 1, its steps are as follows: 1) Add the dispersed phase A into distilled water at -20°C to 50°C, and react for 12h-48h under stirring; then stop the stirring reaction, let stand, and pour out the supernatant; The dispersed phase A is a polymer produced by the polymerization reaction of the conductive polymer monomer, the oxidant and the dopant; the molar ratio of the conductive polymer monomer, the oxidant and the dopant in the dispersed phase A is 1 :2-7.5:10-20; The conductive polymer monomer is 3,4-ethylenedioxythiophene, aniline monomer or pyrrole monomer; The oxidant is sodium persulfate, ammonium persulfate or ferric chloride; or a mixture of sodium persulfate and ferric chloride; or a mixture of ammonium persulfate and ferric sulfate; The dopant is poly(p-styrenesulfonic acid) or a water-soluble salt of poly(p-styrenesulfonic acid); 2) Add post-processing agent to the system, continue to react under stirring, after the reaction is complete, filter to obtain a high-conductivity conductive polymer aqueous dispersion; The weight ratio of the distilled water to the dispersed phase A and the post-treatment agent B is 69-20:30-70:1-10. 3. the purposes of a kind of high-conductivity conductive polymer aqueous dispersion liquid described in claim 1, it is characterized in that, it is used for preparing conductive film by spin spraying or smearing. 4. The application of the high-conductivity conductive polymer aqueous dispersion according to claim 1, characterized in that, it is mixed with a polymer material solution as an additive for conductive materials. 5. the purposes of a kind of high-conductivity conductive polymer aqueous dispersion liquid described in claim 1, it is characterized in that, it is used for preparing electronic device material, electroluminescent material, electrochromic material, antistatic material, electromagnetic shielding material , absorbing materials, anti-corrosion materials or conductive fiber materials.

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