A device and method for preparing ternary conductive polymer composite nanofibers

Abstract

The application provides a preparation method of ternary conductive polymer composite nanofiber, mainly including the following steps: introducing aniline monomer containing a dopant, an initiator of the aniline monomer, a pyrrole monomer, and an initiator of the pyrrole monomer into different nodes in the same reaction tube by the action of gravity; mixing and flowing in the reaction tube and generating a polymerization reaction; in the flowing process, the aniline is polymerized to generate polyaniline nanofiber, then the pyrrole is polymerized on the surface of the polyaniline nanofiber, and finally the thiophene is polymerized on the surface of the composite nanofiber to generate polyaniline / poly pyrrole / poly thiophene ternary composite nanofiber; the polyaniline / poly pyrrole / poly thiophene ternary composite nanofiber is prepared for the first time, and continuous preparation is realized; only the gravity of the solution is used as a power source, without any power device and stirring device, the operation is simple, the production efficiency is greatly improved, and the method is an effective way for industrialized continuous production of ternary conductive polymer composite nanofiber.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of preparation of multi-component composite fiber materials, and particularly relates to a preparation method of ternary conductive polymer composite nanofiber. BACKGROUND

[0002] As important conductive polymer materials, polyaniline, polypyrrole and polythiophene have the characteristics of cheap and easy-to-obtain raw materials, convenient synthesis, high electrical conductivity, good environmental stability and unique doping / dedoping mechanism, and show high application potential in the fields of supercapacitors, chemical sensors, nano-optoelectronic devices, adsorption materials, corrosion-resistant materials and the like. However, the single-component conductive polymer has certain deficiencies in the actual application process, such as polyaniline is suitable for acid electrolyte, and polypyrrole is suitable for neutral electrolyte and alkaline electrolyte. Therefore, the organic combination of polyaniline, polypyrrole and polythiophene to prepare ternary composite nanofiber not only can maintain the flexibility of conductive polymer, but also can greatly exhibit the synergistic effect between different components, and at the same time, combined with the size effect of nanofiber, can provide a reliable path for preparing flexible electrode materials with high conductivity and high energy storage performance.

[0003] Currently, there are few related works on polyaniline / polyazole / polythiophene ternary composite nanofibers, and no patent has been reported on the continuous preparation method thereof. More works mainly focus on the preparation of single conductive polymer or binary composite nanofibers of conductive polymers. The synthesis methods of conductive polymer nanofibers mainly include electrochemical method and chemical oxidation method, in addition, the nanofibers can also be prepared by electrospinning [CN100360725C, CN101973713A, CN101967279A], mechanical stretching and other methods. The electrochemical method is to dissolve monomers in an electrolyte and directly polymerize on an inert electrode under the action of an electric field. This method needs to use expensive instruments and equipment, and the yield is limited by the electrode area, which limits the scale production and application. The chemical method does not need to use electrochemical equipment, mainly including template method and template-free method. The template method is to limit the polymerization growth of conductive polymers by adding hard templates such as zeolite, porous membrane, porous alumina membrane or soft templates such as surfactant and alcohol to the system, so that the conductive polymers grow along the specific template pore direction, and then induce the synthesis of conductive polymer nanofibers [CN101284908A, CN100586987C]. This method needs to remove the template in most cases, and the post-processing process is relatively complicated. At the same time, the removal of the template will cause certain damage to the structure of the conductive polymer. The template-free method effectively makes up for this defect, mainly including emulsion polymerization [CN102060993A, CN102050947A], interfacial polymerization [CN101016660A, CN100497440C, CN101710541A, CN100480443C, CN101037504A], ultrasonic polymerization [CN1323199C] and the like, but these methods also have certain limitations, such as the need to use a large amount of emulsifier, organic solvent, the yield is limited by the interface area, it is difficult to realize scale production, it needs to use ultrasonic equipment, and the product morphology size, structure order and performance need to be further improved. At present, the reported conductive polymer binary composite materials are mainly synthesized by two-step or multi-step method [CN107794600A], and the existence of each offline link not only greatly reduces the synthesis efficiency, but also may affect the further ordered growth of the conductive polymer, so that the performance of the final product still has a large space for improvement.

[0004] Based on this, the polyaniline / polyazole / polythiophene ternary composite nanofiber is first constructed, and a new method for realizing one-step continuous preparation thereof by gravity is provided. SUMMARY

[0005] In view of the problems in the prior art, the application provides a continuous preparation device and method of ternary conductive polymer composite nanofiber, which only introduces aniline monomer solution and aniline monomer initiator solution into the same pipeline in a fluid free-flowing manner, the two solutions are fully mixed and flow polymerization is performed in the pipeline to generate polyaniline nanofiber; then pyrrole monomer solution and pyrrole monomer initiator solution are introduced into the continuously flowing system to combine with the polyaniline nanofiber to generate polyaniline / poly pyrrole composite nanofiber; finally, thiophene monomer solution and thiophene monomer initiator solution are introduced into the continuously flowing system to combine with the polyaniline / poly pyrrole composite nanofiber to generate highly ordered and excellent performance polyaniline / poly pyrrole / poly thiophene ternary conductive polymer composite nanofiber.

[0006] To solve the above technical problems, the application adopts the following technical solutions:

[0007] The application provides a preparation device of ternary conductive polymer composite nanofiber, which comprises monomer container A and its initiator container B, monomer container C and its initiator container D, and monomer container E and its initiator container F, wherein the above containers are connected with a main pipeline through branch pipelines, a branch pipeline throttle valve is arranged on each branch pipeline, and the connection points of the branch pipelines and the main pipeline divide the main pipeline into three sections, namely, section I, section II and section III, and a main pipeline throttle valve is arranged on each section.

[0008] Preferably, the monomer container A and its initiator container B, the monomer container C and its initiator container D, and the monomer container E and its initiator container F are sequentially arranged from top to bottom, the monomer container A and its initiator container B are located at the same height, the monomer container C and its initiator container D are located at the same height, the monomer container E and its initiator container F are located at the same height, and the connection points of each monomer container and its initiator container and the main pipeline are located at the same height.

[0009] Preferably, the main pipeline throttle valves are arranged at the lower parts of the three sections, respectively.

[0010] Preferably, the total length of the main pipeline is 3-8 m, and the inner diameter is 0.003-0.02 m.

[0011] Preferably, the length ratio of the three sections of the main pipeline is 1:(1-3):(1-6).

[0012] Preferably, the materials of the containers and the pipelines are acid- and alkali-resistant materials such as polytetrafluoroethylene resin, phenolic resin or organic silicon monomer resin.

[0013] Preferably, the opening and closing degrees of the main pipeline throttle valves in the three sections of the main pipeline can ensure the stable flow of the fluid and effectively control the flow speed of the fluid.

[0014] Preferably, the device can be used for preparing ternary conductive polymer composite nanofiber materials for oxidative polymerization reaction, and the device provided by the application can realize continuous preparation, including but not limited to polyaniline / polyazole / polythiophene composite nanofiber.

[0015] The application further provides a method for preparing ternary conductive polymer composite nanofiber by using the continuous preparation device, and the steps are as follows:

[0016] (1) The aniline monomer solution containing a dopant and the aniline monomer initiator solution are respectively injected into the monomer container A and the initiator container B, the pyrrole monomer solution containing a dopant and the pyrrole monomer initiator solution are respectively injected into the monomer container C and the initiator container D, and the thiophene monomer solution containing a dopant and the thiophene monomer initiator solution are respectively injected into the monomer container E and the initiator container F;

[0017] (2) The branch throttle valves on the branches where the monomer container A and the initiator container B are located are adjusted, so that the aniline monomer solution and the aniline monomer initiator solution are allowed to flow into the main pipeline I segment under the action of gravity and are fully mixed and polymerized in the pipeline to generate polyaniline nanofiber; the branch throttle valves on the branches where the monomer container C and the initiator container D are located are adjusted, so that the pyrrole monomer solution and the pyrrole monomer initiator solution are allowed to flow into the main pipeline II segment under the action of gravity and are reacted in the region to generate polyaniline / polyazole binary composite nanofiber; and the branch throttle valves on the branches where the monomer container E and the initiator container F are located are adjusted, so that the thiophene monomer solution and the thiophene monomer initiator solution are allowed to flow into the main pipeline III segment under the action of gravity and are reacted in the region to generate polyaniline / polyazole / polythiophene ternary composite nanofiber.

[0018] (3) After the reaction is completed, the product is washed, filtered and dried, and finally high-quality polyaniline / polyazole / polythiophene ternary composite nanofiber is obtained.

[0019] Preferably, the molar concentration of the aniline, pyrrole and thiophene monomer solution is 0.03-2 mol / L, and the molar ratio of the aniline, pyrrole and thiophene monomer is 1:(0.4-6):(0.3-4).

[0020] Preferably, the molar ratio of the aniline, pyrrole and thiophene monomer to the initiator thereof is 1:(0.2-4), 1:(0.4-4) and 1:(0.5-6) respectively.

[0021] Preferably, the dopant is single or complex dopant such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid, sulfosalicylic acid, saturated fatty acid, camphor sulfonic acid and dodecylbenzenesulfonic acid.

[0022] Preferably, the aniline and pyrrole monomer initiator is one or more of ferric trichloride, hydrogen peroxide, ammonium persulfate, formic peroxide, azobis isobutyronitrile, potassium dichromate, etc.; the thiophene monomer initiator is at least two of ferric trichloride, hydrogen peroxide, ammonium persulfate, potassium dichromate, etc.

[0023] Preferably, the order of adding the aniline monomer solution containing a dopant and the aniline monomer initiator solution, the pyrrole monomer solution containing a dopant and the pyrrole monomer initiator solution, and the thiophene monomer solution containing a dopant and the thiophene monomer initiator solution is not limited to injecting the aniline monomer solution containing a dopant and the aniline monomer initiator solution into the monomer container A and the initiator container B, the pyrrole monomer solution containing a dopant and the pyrrole monomer initiator solution into the monomer container C and the initiator container D, and the thiophene monomer solution containing a dopant and the thiophene monomer initiator solution into the monomer container E and the initiator container F, and the order of the three groups of solutions can be arbitrarily changed to prepare different ternary conductive polymer composite nanofibers.

[0024] The synthesis mechanism of the present application is as follows: the present application proposes that only by means of gravity, the space limiting effect of the pipeline, and by sequentially introducing the aniline monomer and its initiator solution, the pyrrole monomer and its initiator solution, and the thiophene monomer and its initiator solution into the main pipeline through the respective branch pipelines, the monomer solutions and the initiator solutions are fully mixed in the main pipeline and flow polymerization is carried out, so that the polyaniline nanofiber, the polyaniline / polyazole binary composite nanofiber, and the polyaniline / polyazole / polythiophene ternary composite nanofiber are sequentially generated in the main pipeline; in the flow process, the polymer continuously grows in orientation under the induction of the flow driving force, and finally the ternary conductive polymer composite nanofiber with uniform morphology, regular structure, and high orientation degree is continuously prepared.

[0025] The beneficial effects of the present application are as follows:

[0026] (1) The present application first organically integrates polyaniline, polyazole, and polythiophene in a one-step method, and proposes a continuous preparation method for preparing polyaniline / polyazole / polythiophene ternary single-point polymer composite nanofiber; the present application only uses gravity as the source of flow power, realizes the dual purposes of fully mixing and flow polymerization of the reaction solution in the pipeline, effectively avoids the use of power devices such as propelling pumps and peristaltic pumps, and mixing and stirring devices, not only greatly simplifies the operation complexity, but also reduces the preparation cost; due to the space limiting effect in the pipeline, the conductive polymer is subjected to a high flow driving force in the growth process, which can effectively induce the oriented growth and ordered assembly of the polymer molecular chain, and provides a strong guarantee for the formation of the highly ordered and high regularity nanofiber structure; the flow rate and flow polymerization time of the reaction solution can be accurately adjusted by the pipeline diameter, length, and throttle valve, which can ensure the stable flow environment of the reaction solution.

[0027] (2) The application has the advantages of simple operation, low cost, high synthesis efficiency, no need to use any template and organic solvent, no need for complicated post-processing process, no need for instrument equipment, high continuity and repeatability, easy batch production, high industrial application potential, one-dimensional preparation process, convenient real-time monitoring of each polymerization growth point, and contribution to the study of structure dynamic evolution mechanism; the addition sequence of the three groups of monomer and initiator solution can be interchanged, and the one-dimensional composite of other polymers can also be used for reference, and the application has high universality.

[0028] (3) The polyaniline / polyazole / polythiophene ternary composite nanofiber obtained by the application has uniform morphology, regular structure, high order degree, good dispersity and excellent performance, and can be applied to energy storage and conversion materials, conductive materials, antistatic materials, sensing materials, adsorption materials, corrosion-resistant materials and many other fields. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 It is a schematic diagram of a polyaniline / polyazole / polythiophene ternary composite nanofiber preparation device.

[0030] Figure 2 It is a scanning electron microscope image of the nylon / polyazole / polythiophene composite fiber synthesized in Example 1 of the application.

[0031] Figure 3 It is a cyclic voltammogram of the polyaniline / polyazole / polythiophene ternary composite nanofiber synthesized in Example 2 of the application at a scanning rate of 5 mV / s in 1 mol / L sulfuric acid electrolyte.

[0032] Figure 4 It is a scanning electron microscope image of the nylon / polyazole / polythiophene composite fiber synthesized in Example 3 of the application.

[0033] Figure 5 It is a constant current charge-discharge curve of the polyaniline / polyazole / polythiophene ternary composite nanofiber synthesized in Example 4 of the application at a scanning rate of 2 A / g in 1 mol / L sulfuric acid electrolyte.

[0034] Figure 6 It is a scanning electron microscope image of the nylon / polyazole / polythiophene composite fiber synthesized in Example 5 of the application.

[0035] Figure 7 It is an alternating current impedance curve of the polyaniline / polyazole / polythiophene ternary composite nanofiber synthesized in Example 6 of the application in 1 mol / L sulfuric acid electrolyte. DETAILED DESCRIPTION

[0036] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0037] Example 1

[0038] like Figure 1 As shown, the continuous preparation device for ternary conductive polymer composite nanofibers of the present invention includes a monomer container A (1) and its initiator container B (2), a monomer container C (3) and its initiator container D (4), a monomer container E (5) and its initiator container F (6). All of the above containers are connected to the main pipeline (8) through branch pipes. Each reaction branch pipe is equipped with a branch pipe throttle valve (7). The branch pipe connection point divides the main pipeline into three sections: I, II, and III. Each section is equipped with a main pipe throttle valve (9). The total length of the main pipeline is 3 m, and the inner diameter is 0.003 m. The length ratio of the three sections I, II, and III of the main pipeline is 1:1:2.

[0039] The method for preparing ternary conductive polymer composite nanofibers using the above-described continuous preparation apparatus in this embodiment is as follows:

[0040] (1) Weigh a certain amount of aniline and ammonium persulfate and dissolve them in 1 mol / L hydrochloric acid solution to prepare 0.03 mol / L aniline solution and 0.06 mol / L ammonium persulfate solution respectively, and inject them into monomer container A and initiator container B respectively; Weigh a certain amount of pyrrole and ferric chloride and dissolve them in 1 mol / L hydrochloric acid solution to prepare 0.03 mol / L pyrrole solution and 0.06 mol / L ferric chloride solution respectively, and inject them into monomer container C and initiator container D respectively; Weigh a certain amount of thiophene, ferric chloride and ammonium persulfate and dissolve them in 1 mol / L hydrochloric acid solution to prepare 0.03 mol / L thiophene solution and 0.1 mol / L ferric chloride and ammonium persulfate mixture respectively, and inject them into monomer container E and initiator container F respectively.

[0041] (2) Adjust the branch throttle valves corresponding to monomer container A and initiator container B to make aniline solution and ammonium persulfate solution flow freely into main pipeline I section and fully mix and flow polymerize in the pipeline; adjust the branch throttle valves corresponding to monomer container C and initiator container D to make pyrrole solution and ferric trichloride solution flow freely into main pipeline II section and flow polymerize; adjust the branch throttle valves corresponding to monomer container E and initiator container F to make thiophene solution, ferric trichloride and ammonium persulfate mixed solution flow freely into main pipeline III section and flow polymerize; during the period, adjust the main pipeline throttle valves in the three sections of main pipeline I, II and III to ensure stable flow of the fluid and effectively control the flow rate of the fluid; after sufficient reaction, wash, filter and dry the product to finally obtain ternary polyaniline / polypryrrole / polythiophene composite nanofiber with a diameter of 20-60 nm and a length of 150-400 nm (see Figure 2 ).

[0042] Example 2

[0043] The total length of the main pipeline in the continuous preparation device of ternary conductive polymer composite nanofiber of this example is 3.5 m, the inner diameter is 0.008 m, the length ratio of the three sections of main pipeline I, II and III is 1:2:3, and the other implementation modes are the same as those of example 1.

[0044] The method for preparing ternary conductive polymer composite nanofiber by using the above continuous preparation device in this example is as follows:

[0045] (1) A certain amount of aniline, hydrogen peroxide and ammonium persulfate are respectively dissolved in 1 mol / L sulfuric acid solution to prepare 0.1 mol / L aniline solution, 0.05 mol / L hydrogen peroxide and ammonium persulfate mixed solution, which are respectively injected into monomer container A and initiator container B; a certain amount of pyrrole and ferric trichloride are respectively dissolved in 1 mol / L sulfuric acid solution to prepare 0.04 mol / L pyrrole solution and 0.02 mol / L ferric trichloride solution, which are respectively injected into monomer container C and initiator container D; a certain amount of thiophene, ammonium persulfate and hydrogen peroxide are respectively dissolved in 1 mol / L sulfuric acid solution to prepare 0.03 mol / L thiophene solution, 0.015 mol / L ammonium persulfate and hydrogen peroxide mixed solution, which are respectively injected into monomer container E and initiator container F;

[0046] (2) Adjust the branch throttle valves corresponding to monomer container A and initiator container B to make the aniline monomer solution, hydrogen peroxide and ammonium persulfate mixture flow freely into the main pipeline I section and fully mix and flow polymerize in the pipeline; adjust the branch throttle valves corresponding to monomer container C and initiator container D to make the pyrrole monomer solution and ferric chloride solution flow freely into the main pipeline II section and flow polymerize; adjust the branch throttle valves corresponding to monomer container E and initiator container F to make the thiophene monomer solution, ammonium persulfate and hydrogen peroxide mixture flow freely into the main pipeline III section and flow polymerize, during which, the main pipeline throttle valves in the three sections of the main pipeline I, II and III are adjusted to ensure stable fluid flow and effectively control the fluid flow rate; after sufficient reaction, the product is washed, filtered and dried to finally obtain high-quality poly-aniline / poly-pyrrole / poly-thiophene ternary composite nanofiber, and the cyclic voltammogram of the composite nanofiber as an electrode in 1 mol / L sulfuric acid electrolyte at a scanning rate of 5 mV / s is as shown in Figure 3 The specific capacitance is 958.2 F / g.

[0047] Example 3

[0048] The total length of the main pipeline in the continuous preparation device of the ternary conductive polymer composite nanofiber of this example is 4 m, the inner diameter is 0.12 m, the length ratio of the three sections of the main pipeline I, II and III is 1:3:2, and the other implementation manners are the same as those of Example 1.

[0049] The method for preparing the ternary conductive polymer composite nanofiber by using the above continuous preparation device in this example is as follows:

[0050] (1) A certain amount of aniline, potassium dichromate and ferric chloride are respectively dissolved in 1 mol / L sulfosalicylic acid solution to prepare 0.2 mol / L aniline solution, 0.5 mol / L potassium dichromate and ferric chloride mixture, and are respectively injected into monomer container A and initiator container B; a certain amount of pyrrole and hydrogen peroxide are respectively dissolved in 1 mol / L hydrochloric acid solution to prepare 1.2 mol / L pyrrole solution and 0.5 mol / L hydrogen peroxide solution, and are respectively injected into monomer container C and initiator container D; a certain amount of thiophene, ammonium persulfate and ferric chloride are respectively dissolved in 1 mol / L sulfosalicylic acid solution to prepare 0.8 mol / L pyrrole solution, 0.5 mol / L ammonium persulfate and ferric chloride mixture, and are respectively injected into monomer container E and initiator container F;

[0051] (2) Adjust the branch throttle valves corresponding to monomer container A1 and initiator container B2 to make the aniline monomer solution, potassium dichromate and ferric chloride mixed solution flow freely into the main pipeline I section and fully mix and flow polymerize in the pipeline; adjust the branch throttle valves corresponding to monomer container C and initiator container D to make the pyrrole monomer solution and hydrogen peroxide solution flow freely into the main pipeline II section and flow polymerize; adjust the branch throttle valves corresponding to monomer container E and initiator container F to make the thiophene monomer solution, ammonium persulfate and ferric chloride mixed solution flow freely into the main pipeline III section and flow polymerize, during which, the main pipeline throttle valves in the three sections of the main pipeline I, II and III are adjusted to ensure stable flow of the fluid and effectively control the flow rate of the fluid; after sufficient reaction, the product is washed, filtered and dried, and finally the ternary conductive polymer composite nanofiber with a diameter of 30-70 nm and a length of 150-450 nm is obtained (see Figure 4 ).

[0052] Example 4

[0053] The total length of the main pipeline in the continuous preparation device of the ternary conductive polymer composite nanofiber of this example is 8 m, the inner diameter is 0.02 m, the length ratio of the three sections of the main pipeline I, II and III is 1:3:4, and the other implementation modes are the same as those of Example 1.

[0054] The method for preparing the ternary conductive polymer composite nanofiber by using the above continuous preparation device in this example is as follows:

[0055] (1) A certain amount of aniline and azobisisobutyronitrile are respectively dissolved in 1 mol / L acetic acid solution to prepare 1 mol / L aniline solution and 2 mol / L azobisisobutyronitrile solution, which are respectively injected into monomer container A and initiator container B; a certain amount of pyrrole and ammonium persulfate are respectively dissolved in 1 mol / L nitric acid solution to prepare 1.5 mol / L pyrrole solution and 3 mol / L ammonium persulfate solution, which are respectively injected into monomer container C and initiator container D; a certain amount of thiophene, ferric chloride and potassium dichromate are respectively dissolved in 1 mol / L dodecylbenzenesulfonic acid solution to prepare 1.8 mol / L thiophene solution, 4 mol / L ferric chloride and potassium dichromate mixed solution, which are respectively injected into monomer container E and initiator container F;

[0056] (2) Adjust the branch throttle valves corresponding to monomer container A and initiator container B to make the aniline monomer solution and azobisisobutyronitrile solution flow freely into the main pipeline I section and fully mix and flow polymerize in the pipeline; adjust the branch throttle valves corresponding to monomer container C and initiator container D to make the pyrrole monomer solution and ammonium persulfate solution flow freely into the main pipeline II section and flow polymerize; adjust the branch throttle valves corresponding to monomer container E and initiator container F to make the thiophene monomer solution, iron trichloride and potassium dichromate mixed solution flow freely into the main pipeline III section and flow polymerize, during which, the main pipeline throttle valves in the three section areas of the main pipeline I, II and III are adjusted to ensure stable flow of the fluid and effectively control the flow rate of the fluid; after sufficient reaction, the product is washed, filtered and dried to finally obtain high-quality poly-aniline / poly-pyrrole / poly-thiophene ternary composite nanofiber. The constant current charge-discharge curve of the composite nanofiber at a scanning rate of 2 A / g in a 1 mol / L sulfuric acid electrolyte is as shown in Figure 5 The specific capacitance is 756.4 F / g.

[0057] Example 5

[0058] The total length of the main pipeline in the continuous preparation device of the ternary conductive polymer composite nanofiber of this example is 6 m, the inner diameter is 0.015 m, the length ratio of the three section areas of the main pipeline I, II and III is 1:3:6, and the other implementation manners are the same as those in Example 1.

[0059] The method for preparing the ternary conductive polymer composite nanofiber by using the above continuous preparation device in this example is as follows:

[0060] (1) A certain amount of aniline and potassium dichromate are respectively dissolved in 1 mol / L nitric acid solution to prepare 1.5 mol / L aniline solution and 4.5 mol / L potassium dichromate solution, which are respectively injected into monomer container A and initiator container B; a certain amount of pyrrole and azobisisobutyronitrile are respectively dissolved in 1 mol / L hydrochloric acid solution to prepare 0.9 mol / L pyrrole solution and 1.8 mol / L azobisisobutyronitrile solution, which are respectively injected into monomer container C and initiator container D; a certain amount of thiophene, hydrogen peroxide and potassium dichromate are respectively dissolved in 1 mol / L acetic acid solution to prepare 1.2 mol / L thiophene solution, 6 mol / L hydrogen peroxide and potassium dichromate mixed solution, which are respectively injected into monomer container E and initiator container F;

[0061] (2) Adjust the branch throttle valves corresponding to monomer container A and initiator container B to make the aniline monomer solution and potassium dichromate solution flow freely into the main pipeline I section and fully mix and flow polymerization in the pipeline; adjust the branch throttle valves corresponding to monomer container C and initiator container D to make the pyrrole monomer solution and azobisisobutyronitrile solution flow freely into the main pipeline II section and flow polymerization; adjust the branch throttle valves corresponding to monomer container E and initiator container F to make the thiophene monomer solution, hydrogen peroxide and potassium dichromate mixed solution flow freely into the main pipeline III section and flow polymerization, during which, the main pipeline throttle valves in the three section areas of the main pipeline I, II and III are adjusted to ensure stable flow of the fluid and effectively control the flow rate of the fluid; after sufficient reaction, the product is washed, filtered and dried, and finally the ternary polyaniline / polyazole / polythiophene composite nanofiber with a diameter of 30-80 nm and a length of 200-500 nm is obtained (see Figure 6 ).

[0062] Example 6

[0063] The total length of the main pipeline in the continuous preparation device of the ternary conductive polymer composite nanofiber of this example is 5 m, the inner diameter is 0.01 m, the length ratio of the three section areas of the main pipeline I, II and III is 1:2:4, and the other implementation manners are the same as those in Example 1.

[0064] The method for preparing the ternary conductive polymer composite nanofiber by using the above continuous preparation device in this example is as follows:

[0065] (1) A certain amount of aniline and peroxycarbonyl are dissolved in a mixed solution of 1 mol / L sulfuric acid and hydrochloric acid, respectively, to prepare a 1.2 mol / L aniline solution and a 4.8 mol / L ferric trichloride solution, which are respectively injected into monomer container A and initiator container B; a certain amount of pyrrole, ferric trichloride and ammonium persulfate are dissolved in a mixed solution of 1 mol / L sulfuric acid and hydrochloric acid, respectively, to prepare a 1.5 mol / L pyrrole solution, a 6 mol / L ferric trichloride and ammonium persulfate mixed solution, which are respectively injected into monomer container C and initiator container D; a certain amount of thiophene, potassium dichromate and ammonium persulfate are dissolved in a mixed solution of 1 mol / L camphor sulfonic acid and hydrochloric acid, respectively, to prepare a 1 mol / L thiophene solution, a 6 mol / L potassium dichromate and ammonium persulfate mixed solution, which are respectively injected into monomer container E and initiator container F;

[0066] (2) Adjust the branch throttle valve corresponding to monomer container A and initiator container B, so that the aniline monomer solution and the ferric chloride solution flow freely into the main pipeline I section and fully mix and flow polymerization in the pipeline; adjust the branch throttle valve corresponding to monomer container C and initiator container D, so that the pyrrole monomer solution, ferric chloride and ammonium persulfate mixed solution flow freely into the main pipeline II section and flow polymerization; adjust the branch throttle valve corresponding to monomer container E and initiator container F, so that the thiophene monomer solution, potassium dichromate and ammonium persulfate mixed solution flow freely into the main pipeline III section and flow polymerization, during which, the main pipeline I, II, III three section area main pipe throttle valve is adjusted to ensure stable flow of the fluid, and effectively control the flow rate of the fluid; after sufficient reaction, the product is washed, filtered and dried, and finally high-quality polyaniline / polyazole / polythiophene ternary composite nanofiber is obtained, and the alternating current impedance curve of the composite nanofiber in 1 mol / L sulfuric acid electrolyte is as shown in Figure 7 ​

Claims

1. A device for preparing ternary conductive polymer composite nanofibers, characterized in that: The system includes a single container A (1) and its initiator container B (2), a single container C (3) and its initiator container D (4), a single container E (5) and its initiator container F (6). All of these containers are connected to the main pipeline (8) through branch pipes. Each branch pipe is equipped with a branch pipe throttle valve (7). The connection point between the branch pipe and the main pipeline (8) divides the main pipeline (8) into three sections: I, II, and III. Each section is equipped with a main pipe throttle valve (9). The total length of the main pipeline is 3 to 8 m, and the inner diameter is 0.003 to 0.02 m. The length ratio of the three sections I, II, and III of the main pipeline is 1:(1 to 3):(1 to 6). By adjusting the opening and closing degree of the main pipe throttle valves in the three sections I, II, and III of the main pipeline, the fluid can be kept stable and the flow rate can be effectively controlled.

2. The apparatus for preparing ternary conductive polymer composite nanofibers according to claim 1, characterized in that: The containers and pipes are made of acid and alkali resistant materials, including polytetrafluoroethylene resin, phenolic resin or organosilicon monomer resin.

3. The method for preparing ternary conductive polymer composite nanofibers using the preparation apparatus according to any one of claims 1 or 2, characterized in that... Includes the following steps: (1) The doped aniline monomer solution and the aniline monomer initiator solution are injected into monomer container A (1) and initiator container B (2) respectively. The doped pyrrole monomer solution and the pyrrole monomer initiator solution are injected into monomer container C (3) and initiator container D (4) respectively. The doped thiophene monomer solution and the thiophene monomer initiator solution are injected into monomer container E (5) and initiator container F (6) respectively. (2) Adjust the branch pipe throttle valves on the branch pipes where monomer container A (1) and initiator container B (2) are located, so that the aniline monomer solution and aniline monomer initiator solution flow freely into the main pipe section I under gravity, and are fully mixed and polymerized in the pipe to generate polyaniline nanofibers; adjust the branch pipe throttle valves on the branch pipes where monomer container C (3) and initiator container D (4) are located, so that the pyrrole monomer solution and pyrrole monomer initiator solution flow freely into the main pipe section II under gravity, and react in this area to generate polyaniline / polypyrrole binary composite nanofibers; adjust the branch pipe throttle valves on the branch pipes where monomer container E (5) and initiator container F (6) are located, so that the thiophene monomer solution and thiophene monomer initiator solution flow freely into the main pipe section III under gravity, and react in this area to generate polyaniline / polypyrrole / polythiophene ternary composite nanofibers; (3) After the reaction is complete, the product is washed, filtered and dried to obtain polyaniline / polypyrrole / polythiophene ternary conductive polymer composite nanofibers.

4. The method for preparing ternary conductive polymer composite nanofibers according to claim 3, characterized in that: The molar concentration of the aniline, pyrrole, and thiophene monomer solution is 0.03~1.8 mol / L, and the monomer molar ratio is 1:(0.4~6):(0.3~4).

5. The method for preparing ternary conductive polymer composite nanofibers according to claim 3, characterized in that: The molar ratios of the aniline, pyrrole, and thiophene monomers to their initiators are 1:(0.5~4), 1:(0.417~4), and 1:(0.5~6), respectively.

6. The method for preparing ternary conductive polymer composite nanofibers according to claim 3, characterized in that: The dopant is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid, sulfosalicylic acid, saturated fatty acid, camphor sulfonic acid, and dodecylbenzene sulfonic acid.

7. The method for preparing ternary conductive polymer composite nanofibers according to claim 3, characterized in that: The initiators for the aniline and pyrrole monomers are one or more of ferric chloride, hydrogen peroxide, ammonium persulfate, formyl peroxide, azobisisobutyronitrile, and potassium dichromate; the initiators for the thiophene monomers are at least two of ferric chloride, hydrogen peroxide, ammonium persulfate, and potassium dichromate.

8. The method for preparing ternary conductive polymer composite nanofibers according to claim 3, characterized in that: The order in which the doped aniline monomer solution and aniline monomer initiator solution, the doped pyrrole monomer solution and pyrrole monomer initiator solution, and the doped thiophene monomer solution and thiophene monomer initiator solution are added is not limited to injecting the doped aniline monomer solution and aniline monomer initiator solution into monomer container A (1) and initiator container B (2), injecting the doped pyrrole monomer solution and pyrrole monomer initiator solution into monomer container C (3) and initiator container D (4), and injecting the doped thiophene monomer solution and thiophene monomer initiator solution into monomer container E (5) and initiator container F (6). The order of the three sets of solutions can be arbitrarily changed to prepare different ternary conductive polymer composite nanofibers.

Images