A rapid self-polymerization polyaniline buffer and a rapid self-polymerization method

Abstract

The present invention belongs to the technical field of polyaniline synthesis, and specifically relates to a rapid self-polymerizing polyaniline buffer and a rapid self-polymerization method. Aniline monomer is dissolved in a water-soluble salt solvent to prepare a polyaniline precursor buffer, which is allowed to stand for self-polymerization at room temperature, and then self-polymerizes and grows on a substrate to form polyaniline. The beneficial effect of the present invention is that a method for preparing a rapid self-polymerizing polyaniline buffer is developed, which does not require an initiator. The polyaniline prepared by the rapid self-polymerization method has excellent conductivity. This buffer can realize large-scale production to prepare conductive polymer polyaniline powder and form a coating with uniform thickness on the surface of the substrate through coating and impregnation processes, and rapidly polymerizes and grows to form a stable and dense polyaniline composite layer. This rapid self-polymerizing polyaniline buffer will have broad application prospects in the fields of supercapacitor electrode materials, electromagnetic shielding, microwave absorption, and metal anti-corrosion coatings.

Description

Technical Field

[0001] The invention belongs to the technical field of polyaniline synthesis, and particularly relates to a rapid self-polymerization polyaniline buffer and a rapid self-polymerization method. Background Art

[0002] Polyaniline (PAI) has become a hot research material in the scientific field due to its excellent electrical conductivity, redox properties, catalytic performance, electrochromic behavior, and good environmental stability. It is one of the most widely studied conductive polymers. Currently, PAI has broad application prospects in new energy electrode materials, optoelectronic devices, biological and chemical sensors, and antistatic properties.

[0003] Polyaniline is generally prepared through two polymerization methods: in-situ chemical oxidation polymerization and electrochemical polymerization. In-situ chemical oxidation polymerization is the main route for synthesizing polyaniline. Usually, an oxidant is used in an acidic medium to cause aniline monomer to undergo oxidative polymerization. Commonly used oxidants include ammonium persulfate ((NH4)2S2O8), potassium persulfate (K2S2O8), hydrogen peroxide (H2O2), potassium permanganate (KMnO4), and ferric chloride (FeCl3). The structure and properties of the final synthesized polyaniline are affected by conditions such as the type and content of the oxidant, the type of acidic medium, the pH value, and the reaction temperature. The electrochemical polymerization method disperses the aniline monomer in an acidic electrolyte and, under the action of an electric field, adjusts the electrochemical parameters to cause the aniline monomer in the electrolyte to undergo oxidative polymerization on the surface of an inert electrode. Common methods include constant potential, constant current, pulse method, and cyclic voltammetry. The product prepared by electrochemical polymerization is highly pure but not suitable for large-scale production. Regardless of the synthesis method, polyaniline (PAI) is insoluble in most organic solvents. This is primarily due to the high molecular rigidity and strong interchain hydrogen bonding of the PAI chain, which results in poor solubility and machinability. This makes it difficult to formulate PAI polymer solutions for coating and lamination, creating inconvenience in subsequent processing and applications, significantly limiting the application of PAI. Furthermore, in-situ chemical oxidative polymerization methods suffer from long reaction times, the morphology and properties of the resulting PAI are affected by the type and amount of oxidant used, the redox state and structural morphology of the resulting PAI are difficult to control, and separation of the PAI from the oxidant is difficult. Summary of the Invention

[0004] Common oxidants such as potassium dicadmium oxide, ferric chloride, potassium permanganate, potassium chlorate and potassium bromate have strong oxidizing properties, but contain heavy metals or other metal ions, which all participate in redox reactions to generate metal oxides or metal salts. They are difficult to post-process in industrial production and are not conducive to obtaining polyaniline with higher purity. The oxidant ammonium persulfate (APS) does not contain metal ions, is easy to post-process, has strong oxidizing ability, but generates a large amount of heat during the polymerization process. The purpose of the present invention is to solve the problems and shortcomings in the prior art and provide a method for preparing a fast self-polymerizing polyaniline buffer. The method does not add an oxidant and performs self-polymerization in a compatible water-soluble salt electrolyte. It is both economical and environmentally friendly. It can not only quickly polymerize and prepare polyaniline powder with high conductivity, but also form a composite coating on the substrate through a uniform coating or impregnation process.

[0005] In order to achieve the purpose of the present invention, the technical solution adopted is:

[0006] The present invention provides a method for preparing a fast self-polymerizing polyaniline buffer solution, wherein the raw materials include the following components in parts by weight:

[0007] 2 to 8 parts by weight of a first completely ionizable salt electrolyte;

[0008] 2 to 8 parts by weight of a second fully ionizable salt electrolyte;

[0009] 60-80 parts by weight of deionized water;

[0010] 2-15 parts by weight of aniline monomer;

[0011] Furthermore, aniline monomer is dissolved in a water-soluble salt solvent to prepare a buffer solution for polymerization to prepare polyaniline powder or polyaniline coating layer precursor. The preparation steps include:

[0012] (1) Weigh the first completely ionizable salt electrolyte and the second completely ionizable salt electrolyte according to the weight ratio, add them into deionized water, stir them thoroughly to completely dissolve them, and the solution becomes transparent.

[0013] (2) Slowly add the aniline monomer solution dropwise and stir rapidly to completely dissolve the aniline monomer to prepare a polyaniline buffer solution of a certain concentration.

[0014] (3) The buffer solution is evenly coated on the substrate or directly immersed in the buffer solution, and allowed to stand at room temperature for a certain period of time, and self-polymerizes and grows to form a polyaniline layer or suspended particles.

[0015] Furthermore, the first completely ionizable salt electrolyte in step (1) is lithium bisulfate (LiHSO4), sodium bisulfate (NaHSO4) or potassium bisulfate (KHSO4); the second completely ionizable salt electrolyte in step (1) is lithium chloride (LiCl), sodium chloride (NaCl) or potassium chloride (KCl). The first completely ionizable salt electrolyte can be completely ionized in aqueous solution to form metal ions, H + and SO4 2- , can form a strong charged ion flow, increasing the ionic conductivity of the electrolyte. + Provide acidity to adjust the pH value of the electrolyte; in addition, SO4 2- The presence of negative ions can form polarons with the protonated nitrogen atoms in the PANI molecular chain (the protonated nitrogen atoms of the quinone imine ion and the protonated nitrogen atoms of the amine ion). After delocalization, the polarons form carriers, thus making the polyaniline conductive. Another function is to prepare acidic solutions with the same pH. The preparation process of powdered water-soluble hydrogen sulfate is simpler and more convenient than concentrated sulfuric acid. Second, fully ionizable salt electrolytes can also be completely ionized in aqueous solution to form metal ions and Cl - , does not affect the redox reaction (metal ions do not participate in the redox reaction), improves the conductivity of the electrolyte, and effectively reduces the charge transfer resistance.

[0016] Furthermore, the concentration of the two completely ionizable salt electrolytes in step (1) is 0.05M to 5M.

[0017] Furthermore, the concentration of the aniline monomer in step (2) is 0.01M to 5M.

[0018] Furthermore, the buffer solution is self-polymerized at 15° C. to 70° C., and after standing for 0.1 h to 8 h, the reaction forms polyaniline suspension particles, which are filtered and washed with water until the pH is neutral (generally around 7), and then dried to obtain green conductive polyaniline powder (generally vacuum dried at 70° C.).

[0019] Furthermore, the buffer solution can be compounded on a substrate by uniform coating or impregnation process, and allowed to stand at 15°C to 70°C, where the buffer solution will self-polymerize, and after 0.1h to 8h, a polyaniline layer will be formed by reaction and grow on the surface of the substrate, which is then washed with water until the pH is neutral (generally around 7), and then dried to obtain a polyaniline composite material (generally dried in vacuum at 70°C).

[0020] Furthermore, the substrate in step (3) can be an inorganic substrate or a polymer film, more preferably a carbon nanotube film. The carbon nanotube film has a high conductivity, reaching 10 3S / cm. The carbon nanotube film contains crisscrossing carbon nanotube fibers and fiber bundles. The diameter of a single carbon nanotube fiber ranges from 20nm to 30nm, and the largest fiber bundle consists of 5 to 8 individual carbon nanotube fibers, with a high aspect ratio. The carbon nanotube fibers and fiber bundles intertwine and entwine with each other, forming a porous framework with excellent flexibility. The surface of the acidified carbon nanotube fibers contains abundant hydroxyl and carboxyl groups. Polyaniline grows uniformly around the axis of the acidified carbon nanotube fibers, ultimately embedding within the porous framework of the carbon nanotube film. Therefore, the carbon nanotube film is preferred.

[0021] Furthermore, the buffer solution does not require an initiator, and the polyaniline prepared by a rapid self-polymerization method has excellent electrical conductivity.

[0022] The present invention has the following beneficial effects:

[0023] The present invention dissolves aniline monomer in a first fully ionizable and a second fully ionizable composite water-soluble salt solvent to prepare a polyaniline buffer solution. No additional initiator is required. After stirring and mixing, high-conductivity polyaniline powder can be stably and rapidly prepared at room temperature. This effectively solves the problems of long reaction time, difficulty in separating the product from the oxidant, and the influence of the type and amount of the oxidant on the morphological structure and performance of polyaniline prepared by in-situ chemical oxidative polymerization. The preparation method of the rapid self-polymerizing polyaniline buffer provided by the present invention is convenient and simple, and the raw materials of each component are readily available and low in cost. In addition, the prepared buffer solution can be uniformly formed into a coating on a substrate through coating and impregnation processes. At room temperature, the surface of the substrate polymerizes and grows to form a stable and dense polyaniline composite layer. The rapidly polymerized polyaniline has strong bonding with the substrate. After the buffer solution is directly applied to the substrate surface, composite applications can be achieved. No initiator is required to be added to this buffer solution, solving the problem of achieving composite on the substrate by dissolving the polyaniline. This fast self-polymerizing polyaniline buffer will have broad application prospects in the fields of supercapacitor electrode materials, electromagnetic shielding, microwave absorption and metal anti-corrosion coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a photo of the polyaniline suspension particles formed by self-polymerization reaction after the buffer solution is left to stand at room temperature in Example 3 of the present invention;

[0025] Figure 2 This is a physical picture of the green conductive polyaniline powder prepared in Example 3 of the present invention;

[0026] Figure 3 This is a scanning electron microscope image of polyaniline prepared in Example 3 of the present invention;

[0027] Figure 4 This is an infrared image of polyaniline prepared in Example 3 of the present invention;

[0028] Figure 5 This is the Raman graph of polyaniline prepared in Example 3 of the present invention;

[0029] Figure 6 This is a photo of the polyaniline / carbon nanotube film prepared by the coating process in Example 9 of the present invention. DETAILED DESCRIPTION

[0030] The present invention is not limited to the following specific embodiments. Based on the disclosure of the present invention, a person skilled in the art may adopt a variety of other specific embodiments to implement the present invention. Any simple changes or modifications made to the design structure and concept of the present invention fall within the scope of protection of the present invention. It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other unless they conflict.

[0031] The present invention is further described in detail below in conjunction with the embodiments:

[0032] Example 1

[0033] The rapid self-polymerizing polyaniline buffer solution is prepared using the following raw material components and operating steps: 13.6g of a first fully ionizable salt electrolyte, KHSO4, and 7.4g of a second fully ionizable salt electrolyte, KCl, are weighed and added to 100.0g of deionized water, stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100ml to form a 1M KHSO4 / KCl solution. 1.86g of aniline monomer solution is then slowly added dropwise to the transparent solution, stirred rapidly to dissolve the aniline monomer, to form a polyaniline buffer solution with a concentration of 1M KHSO4 / KCl / 0.2M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating precursor. The buffer solution is allowed to stand at 25°C to form a polyaniline suspension, which is then filtered, washed with water to a pH of 7, and vacuum-dried at 70°C to obtain a green conductive polyaniline powder.

[0034] Example 2

[0035] The rapid self-polymerizing polyaniline buffer solution is prepared using the following raw material components and operating steps: 13.6g of a first fully ionizable salt electrolyte, KHSO4, and 7.4g of a second fully ionizable salt electrolyte, KCl, are weighed and added to 100.0g of deionized water, stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100ml to prepare a 1M KHSO4 / KCl solution. 1.86g of aniline monomer solution is then slowly added dropwise to the transparent solution, stirred rapidly to dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 1M KHSO4 / KCl / 0.2M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating precursor. The buffer solution is allowed to stand at 50°C to form a polyaniline suspension, which is then filtered, washed with water to a pH of 7, and vacuum-dried at 70°C to obtain a green conductive polyaniline powder.

[0036] Example 3

[0037] The rapid self-polymerizing polyaniline buffer solution is prepared using the following raw material components and operating steps: 12.0 g of a first fully ionizable salt electrolyte, NaHSO4, and 5.85 g of a second fully ionizable salt electrolyte, NaCl, are weighed and added to 100 g of deionized water, stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100 ml to prepare a 1 M NaHSO4 / NaCl solution. 1.86 g of aniline monomer solution is then slowly added dropwise to the transparent solution, stirred rapidly to dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 1 M NaHSO4 / NaCl / 0.2 M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating precursor. The buffer solution is allowed to stand at 25°C to form a polyaniline suspension, which is then filtered, washed with water to a pH of 7, and vacuum-dried at 70°C to obtain a green conductive polyaniline powder.

[0038] Example 4

[0039] The rapid self-polymerizing polyaniline buffer solution is prepared using the following raw material components and operating steps: 12.0 g of a first fully ionizable salt electrolyte, NaHSO4, and 5.85 g of a second fully ionizable salt electrolyte, NaCl, are weighed and added to 100 g of deionized water, stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100 ml to prepare a 1 M NaHSO4 / NaCl solution. 1.86 g of aniline monomer solution is then slowly added dropwise to the transparent solution, stirred rapidly to dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 1 M NaHSO4 / NaCl / 0.2 M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating precursor. The buffer solution is allowed to stand at 50°C to form a polyaniline suspension, which is then filtered, washed with water to a pH of 7, and vacuum-dried at 70°C to obtain a green conductive polyaniline powder.

[0040] Example 5

[0041] The rapid self-polymerizing polyaniline buffer solution is prepared using the following raw material components and operating steps: 24.0 g of a first fully ionizable salt electrolyte, NaHSO4, and 11.7 g of a second fully ionizable salt electrolyte, NaCl, are weighed and added to 100 g of deionized water, stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100 ml to prepare a 2M NaHSO4 / NaCl solution. 1.86 g of aniline monomer solution is then slowly added dropwise to the transparent solution, stirred rapidly to dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 2M NaHSO4 / NaCl / 0.2M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating precursor. The buffer solution is allowed to stand at 25°C to form a polyaniline suspension, which is then filtered, washed with water to a pH of 7, and vacuum-dried at 70°C to obtain a green conductive polyaniline powder.

[0042] Example 6

[0043] The rapid self-polymerizing polyaniline buffer solution is prepared using the following raw material components and operating steps: 24.0g of a first fully ionizable salt electrolyte, NaHSO4, and 11.7g of a second fully ionizable salt electrolyte, NaCl, are weighed and added to 100.0g of deionized water, stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100ml to prepare a 2M NaHSO4 / NaCl solution. 2.79g of aniline monomer solution is then slowly added dropwise to the transparent solution, stirred rapidly to dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 2M NaHSO4 / NaCl / 0.3M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating precursor. The buffer solution is allowed to stand at 25°C to form a polyaniline suspension, which is then filtered, washed with water to a pH of 7, and vacuum-dried at 70°C to obtain a green conductive polyaniline powder.

[0044] Example 7

[0045] The rapid self-polymerizing polyaniline buffer solution is prepared using the following raw material components and operating steps: 24.0 g of a first fully ionizable salt electrolyte, NaHSO4, and 11.7 g of a second fully ionizable salt electrolyte, NaCl, are weighed and added to 100 g of deionized water, stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100 ml to prepare a 2M NaHSO4 / NaCl solution. 2.79 g of aniline monomer solution is then slowly added dropwise to the transparent solution, stirred rapidly to dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 2M NaHSO4 / NaCl / 0.3M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating precursor. The buffer solution is allowed to stand at 50°C to form a polyaniline suspension, which is then filtered, washed with water to a pH of 7, and vacuum-dried at 70°C to obtain a green conductive polyaniline powder.

[0046] Example 8

[0047] The rapid self-polymerization polyaniline buffer solution is prepared using the following raw material components and operating steps: 24.0 g of a first fully ionizable salt electrolyte, NaHSO4, and 11.7 g of a second fully ionizable salt electrolyte, NaCl, are weighed, respectively, and added to 100.0 g of deionized water. The mixture is stirred thoroughly to completely dissolve the compatible salts until transparent, and the volume is adjusted to 100 ml to prepare a 2M NaHSO4 / NaCl solution. 2.79 g of an aniline monomer solution is then slowly added dropwise to the transparent solution, with rapid stirring to completely dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 2M NaHSO4 / NaCl / 0.3M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating layer precursor. The buffer solution was evenly coated on the carbon nanotube film through a coating process using a precision coating machine to form a buffer solution coating with a uniform thickness of 50 μm. At room temperature of 25°C, a stable and dense polyaniline composite layer was formed on the surface of the carbon nanotube film. The polyaniline had a strong bonding force with the carbon nanotube film substrate. After washing with water to a pH of 7 and vacuum drying at 70°C, a polyaniline / carbon nanotube film composite material was obtained.

[0048] Example 9

[0049] The rapid self-polymerization polyaniline buffer solution is prepared using the following raw material components and operating steps: 12.0 g of a first fully ionizable salt electrolyte, NaHSO4, and 5.85 g of a second fully ionizable salt electrolyte, NaCl, are weighed, respectively, and added to 100 g of deionized water. The solution is stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100 ml to prepare a 1 M NaHSO4 / NaCl solution. 1.86 g of aniline monomer solution is then slowly added dropwise to the transparent solution, with rapid stirring to completely dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 1 M NaHSO4 / NaCl / 0.2 M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating layer precursor. The buffer solution was evenly coated on the carbon nanotube film through a coating process using a precision coating machine to form a buffer solution coating with a uniform thickness of 50 μm. At room temperature of 25°C, a stable and dense polyaniline composite layer was formed on the surface of the carbon nanotube film. The polyaniline had a strong bonding force with the carbon nanotube film substrate. After washing with water to a pH of 7 and vacuum drying at 70°C, a polyaniline / carbon nanotube film composite material was obtained.

[0050] Example 10

[0051] The rapid self-polymerization polyaniline buffer solution is prepared using the following raw material components and operating steps: 24.0 g of a first fully ionizable salt electrolyte, NaHSO4, and 11.7 g of a second fully ionizable salt electrolyte, NaCl, are weighed, respectively, and added to 100.0 g of deionized water. The mixture is stirred thoroughly to completely dissolve the compatible salts until transparent, and the volume is adjusted to 100 ml to prepare a 2M NaHSO4 / NaCl solution. 2.79 g of an aniline monomer solution is then slowly added dropwise to the transparent solution, with rapid stirring to completely dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 2M NaHSO4 / NaCl / 0.3M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating layer precursor. The buffer solution was evenly coated on the carbon nanotube film through a coating process using a precision coating machine to form a buffer solution coating with a uniform thickness of 50 μm. At room temperature of 50°C, a stable and dense polyaniline composite layer was formed on the surface of the carbon nanotube film through polymerization growth. The polyaniline had a strong bonding force with the carbon nanotube film substrate. After washing with water to a pH of 7 and vacuum drying at 70°C, a polyaniline / carbon nanotube film composite material was obtained.

[0052] Example 11

[0053] The rapid self-polymerization polyaniline buffer solution is prepared using the following raw material components and operating steps: 27.2g of a first fully ionizable salt electrolyte, KHSO4, and 14.9g of a second fully ionizable salt electrolyte, KCl, are weighed in a weight ratio and added to 100.0g of deionized water. The solution is stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100ml to prepare a 2M KHSO4 / KCl solution. 2.79g of aniline monomer solution is then slowly added dropwise to the transparent solution, with rapid stirring to completely dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 2M KHSO4 / KCl / 0.3M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating layer precursor. The buffer solution was evenly coated on the carbon nanotube film using an impregnation process to form a buffer solution coating with a uniform thickness of 50 μm. At room temperature of 25°C, a stable and dense polyaniline composite layer was polymerized and grown on the surface of the carbon nanotube film. The polyaniline had a strong bonding force with the carbon nanotube film substrate. After washing with water to a pH of 7 and vacuum drying at 70°C, a polyaniline / carbon nanotube film composite material was obtained.

[0054] Comparative Example 1

[0055] The rapid self-polymerization polyaniline buffer solution is prepared using the following raw material components and operating steps: 27.2g of a first fully ionizable salt electrolyte, KHSO4, and 14.9g of a second fully ionizable salt electrolyte, KCl, are weighed in a weight ratio and added to 100.0g of deionized water. The solution is stirred thoroughly to dissolve the compatible salts until transparent, and the volume is adjusted to 100ml to prepare a 2M KHSO4 / KCl solution. 2.79g of aniline monomer solution is then slowly added dropwise to the transparent solution, with rapid stirring to completely dissolve the aniline monomer, to prepare a polyaniline buffer solution with a concentration of 2M KHSO4 / KCl / 0.3M ANI, which is used for rapid self-polymerization to prepare polyaniline powder or a polyaniline coating layer precursor. The buffer solution was evenly coated on the polyurethane film using an impregnation process to form a buffer solution coating with a uniform thickness of 50 μm. At room temperature of 25°C, a stable and dense polyaniline composite layer was polymerized and grown on the surface of the polyurethane film. The polyaniline had a strong bonding force with the polyurethane film substrate. After washing with water to a pH of 7 and vacuum drying at 70°C, a polyaniline / polyurethane film composite material was obtained.

[0056] Comparative Example 2

[0057] A 1cm×2cm continuous reinforced carbon nanotube film was immersed in an acetone / ethanol mixture (ethanol / acetone = 1 vol:1 vol) and ultrasonically treated at room temperature for 2 hours. After rinsing with deionized water, it was dried in a vacuum oven at 80°C for 2 hours. 1.86g of aniline monomer was dropwise added to a three-necked flask containing 100mL of 1.0M HCl solution. The acidified carbon nanotube film was then placed in the solution and stirred for 2 hours under a nitrogen atmosphere in an ice-water bath. Then, 100mL of 1.0M HCl solution containing 4.5g of ammonium persulfate was added dropwise. Polymerization was allowed to proceed for 12 hours with stirring at 100 rpm. Finally, the film was washed with copious amounts of deionized water and rinsed with ethanol to remove oligomers. After rinsing, it was dried in a vacuum oven at 70°C for 12 hours to obtain the corresponding carbon nanotube / PANI composite film.

[0058] The polyaniline and polyaniline composite materials prepared in Examples 1 to 11 and Comparative Examples 1 to 2 were tested for electrical conductivity using a dual-electrical four-probe tester (RTS-9 model, Guangzhou Four-Probe Technology, China).

[0059] Table 1 Comparative performance of Examples 1 to 11 and Comparative Examples 1 to 2

[0060]

[0061]

[0062] The conductivity of polyaniline powder prepared by rapid self-polymerization method is basically 2-10S / cm, and the resistance is 10 -1Ω level. The conductivity of the buffer solution increases after being coated on the substrate, mainly because the conductivity of the substrate is relatively large. The conductivity of the carbon nanotube film is 800-1000S / cm, and the resistance is 10 -3 In Examples 8-11, polyaniline was grown after coating and immersion loading on various substrates, indicating that the buffer of the present invention can be uniformly attached and grown on the surfaces of different substrates through these methods.

[0063] The present invention may be summarized in other specific forms that do not violate the spirit or main features of the present invention. Therefore, no matter from which point of view, the above-mentioned embodiments of the present invention can only be regarded as an explanation of the present invention and cannot limit the present invention. For those skilled in the art, improvements and supplements made without departing from the spirit of the present invention should be regarded as within the scope of protection of the present invention.

Claims

1. A rapid self-polymerizing polyaniline buffer, characterized in that The following components are composed of parts by weight composition: 2 to 8 parts by weight of a first completely ionizable salt electrolyte; 2 to 8 parts by weight of a second fully ionizable salt electrolyte; 60-80 parts by weight of deionized water; 2-15 parts by weight of aniline monomer; The first completely ionizable salt electrolyte is lithium bisulfate, sodium bisulfate or potassium bisulfate; the second completely ionizable salt electrolyte is lithium chloride, sodium chloride or potassium chloride.

2. A method for rapid self-polymerization of polyaniline buffer, characterized in that: The following steps are involved: (1) Weighing the first completely ionizable salt electrolyte and the second completely ionizable salt electrolyte respectively according to the weight ratio, adding them to deionized water, stirring them thoroughly to completely dissolve them, and the solution becomes transparent; (2) slowly adding the aniline monomer solution dropwise and stirring rapidly to completely dissolve the aniline monomer to prepare the fast self-polymerizing polyaniline buffer solution according to claim 1; (3) The buffer solution is evenly coated on the substrate or directly left at room temperature for a certain period of time to self-polymerize and grow to form a polyaniline layer or suspended particles.

3. The rapid self-polymerization method of polyaniline buffer according to claim 2, characterized in that: The concentration of the solution obtained in step (1) is 0.05M to 5M.

4. The rapid self-polymerization method of polyaniline buffer according to claim 2, characterized in that: The concentration of aniline monomer in the polyaniline buffer in step (2) is 0.01M to 5M.

5. The rapid self-polymerization method of polyaniline buffer according to claim 2, characterized in that: The buffer solution is self-polymerized at 15°C to 70°C, and after standing for 0.1h to 8h, polyaniline suspension particles are formed. The particles are filtered, washed with water until the pH is neutral, and then dried to obtain green conductive polyaniline powder. Alternatively, the buffer solution is composited on a substrate by uniform coating or dipping, and is allowed to stand at 15° C. to 70° C. for self-polymerization. After 0.1 to 8 hours, a polyaniline layer is formed on the surface of the substrate, which is then washed with water until the pH is neutral and dried to obtain a polyaniline composite material.

6. The method for rapid self-polymerization of a polyaniline buffer according to claim 2, characterized in that: The substrate in step (3) is a carbon nanotube film.

7. The fast self-polymerizing polyaniline buffer according to claim 1, characterized in that: The buffer solution does not require an initiator, and the polyaniline prepared by a rapid self-polymerization method has excellent conductivity.

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