CN112410924B - Carbon nano tube/conductive polymer composite fiber, continuous preparation method and continuous preparation system thereof - Google Patents

Carbon nano tube/conductive polymer composite fiber, continuous preparation method and continuous preparation system thereof Download PDF

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CN112410924B
CN112410924B CN202011161732.0A CN202011161732A CN112410924B CN 112410924 B CN112410924 B CN 112410924B CN 202011161732 A CN202011161732 A CN 202011161732A CN 112410924 B CN112410924 B CN 112410924B
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conductive polymer
nano tube
composite fiber
carbon nano
carbon
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CN112410924A (en
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吴昆杰
董仕轩
勇振中
张永毅
李清文
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Jiangxi Nanotechnology Research Institute
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D13/00—Complete machines for producing artificial threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments

Abstract

The invention discloses a carbon nano tube/conductive polymer composite fiber, a continuous preparation method and a continuous preparation system thereof. The preparation method comprises the following steps: a floating catalytic CVD method is adopted to enable a carbon source to generate carbon nano tube aerogel through catalytic growth reaction; the carbon nanotube aerogel is contacted with the aqueous solution of the conductive polymer monomer, so that the conductive polymer monomer uniformly permeates into the gaps of the carbon nanotubes, and simultaneously the carbon nanotube aerogel is contracted under the action of the surface tension of the solution, so that the carbon nanotube/conductive polymer monomer composite fiber is prepared; and polymerizing the conductive polymer monomer in the carbon nano tube/conductive polymer monomer composite fiber under the action of the oxidant to generate a conductive polymer, thereby obtaining the carbon nano tube/conductive polymer composite fiber. The polypyrrole in the composite fiber provided by the invention is more uniformly distributed and has higher conductivity; meanwhile, the preparation of the carbon nanotube fiber and the compounding process of polypyrrole can be continuously carried out, so that the process flow is simplified.

Description

Carbon nano tube/conductive polymer composite fiber, continuous preparation method and continuous preparation system thereof
Technical Field
The invention belongs to the technical field of fiber synthesis, relates to a carbon nano tube/conductive polymer composite fiber, a continuous preparation method and a continuous preparation system thereof, and in particular relates to a continuous preparation method and a continuous preparation system of a carbon nano tube/conductive polymer composite fiber based on a floating catalytic CVD method.
Background
The carbon nano tube has the excellent characteristics of light weight, high strength, high conductivity, high thermal stability and the like, so that the carbon nano tube becomes a novel conductive material with great potential for replacing the traditional metal. Because of the electron trajectory transportation characteristic in the carbon nanotubes, the resistance of the carbon nanotubes is very small, so that in conductors such as carbon nanotube fibers, films and the like, the resistance mainly comes from the interface resistance between adjacent carbon tubes.
The existing preparation method of the carbon nano tube/conductive polymer composite fiber adopts a mode of firstly soaking the prefabricated carbon nano tube fiber in a monomer solution and then carrying out polymerization reaction (for example, ryu et al, adv. Mater, 2015,27,3250-3255; chen et al, J. Mater. Chem. A,2013,1,2211-2216), because a large number of gaps/holes from nano scale to micro scale exist between carbon nano tube or tube bundles in the prefabricated carbon nano tube fiber, and the wettability of the carbon nano tube to a common solvent is poor, the monomer solution is difficult to enter the gaps, so that the distribution of conductive polymer formed by subsequent polymerization in the fiber is uneven, and the improvement effect of the conductive performance of the carbon nano tube/conductive polymer composite fiber is affected; in addition, in the prior art, the two processes of preparing the carbon nanotube fiber and preparing the carbon nanotube/conductive polymer composite fiber are independently carried out, and the process complexity is high.
Disclosure of Invention
The invention mainly aims to provide a carbon nano tube/conductive polymer composite fiber, a continuous preparation method and a continuous preparation system thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a continuous preparation method of a carbon nano tube/conductive polymer composite fiber, which comprises the following steps:
a floating catalytic CVD method is adopted to enable a carbon source to generate carbon nano tube aerogel through catalytic growth reaction;
the carbon nanotube aerogel is contacted with an aqueous solution of a conductive polymer monomer, so that the conductive polymer monomer uniformly permeates into a carbon nanotube gap, and simultaneously the carbon nanotube aerogel is contracted under the action of solution surface tension to prepare a carbon nanotube/conductive polymer monomer composite fiber;
under the action of an oxidant, the conductive polymer monomer in the carbon nano tube/conductive polymer monomer composite fiber is subjected to an oxidative polymerization reaction to generate a conductive polymer, so that the carbon nano tube/conductive polymer composite fiber is obtained.
The embodiment of the invention also provides the carbon nano tube/conductive polymer composite fiber prepared by the method.
The embodiment of the invention also provides a continuous preparation system of the carbon nano tube/conductive polymer composite fiber, which comprises the following steps:
the carbon nano tube aerogel preparation device at least comprises a reaction chamber, at least is used for enabling a carbon source and a catalyst to catalyze a growth reaction to generate carbon nano tube aerogel;
the fiber preparation device is at least used for enabling the carbon nano tube aerogel to be in contact with the conductive polymer monomer aqueous solution and performing liquid-induced shrinkage to prepare the carbon nano tube/conductive polymer monomer composite fiber;
the polymerization device is at least used for enabling the conductive polymer monomer in the carbon nano tube/conductive polymer monomer composite fiber to generate conductive polymer through oxidation polymerization reaction, so as to obtain the carbon nano tube/conductive polymer composite fiber; the method comprises the steps of,
and the collecting device is at least used for collecting the generated carbon nano tube/conductive polymer composite fiber.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, a floating catalysis method is adopted to prepare the carbon nanotube aerogel, a monomer solution is adopted to carry out densification in the process of densification of the carbon nanotube aerogel through a solution, because gaps among carbon nanotubes and among bundles in the carbon nanotube aerogel are larger, the monomer solution easily enters the gaps in the densification process, then under the action of the surface tension of liquid, the gaps among the carbon nanotubes and among the bundles are reduced, the carbon nanotube aerogel is contracted to form carbon nanotube/pyrrole composite fibers, and then the carbon nanotube/conductive polymer composite fibers with uniform and high conductivity are obtained through polymerization, cleaning, drying and winding; the polypyrrole in the carbon nano tube/polypyrrole composite fiber is more uniformly distributed, and the carbon nano tube/polypyrrole composite fiber has higher conductivity; meanwhile, the preparation of the carbon nanotube fiber and the compounding process of polypyrrole can be continuously carried out, so that the process flow is simplified.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a continuous preparation system for carbon nanotube/conductive polymer composite fiber according to an exemplary embodiment of the present invention;
FIG. 2 is a photograph of carbon nanotube aerogel of example 2 of the present invention;
FIGS. 3 a-3 b are SEM images of carbon nanotube fibers and carbon nanotube/polypyrrole composite fibers prepared in example 2, respectively;
fig. 4a to 4d are SEM images of the surface and the interior of the carbon nanotube/polypyrrole composite fiber prepared in example 2 and EDS profiles corresponding to N elements, respectively.
Reference numerals illustrate: 1-reaction raw material injection device, 2-carrier gas input device, 3-sealing flange, 4-high temperature reaction furnace tube, 5-high temperature furnace, 6-carbon nano tube aerogel, 7-water seal box, 8-tail gas, 9-water tank, 10-water, 11-carbon nano tube/conductive polymer monomer composite fiber, 12-bent pipe, 13-conductive polymer monomer aqueous solution, 14-fiber guide shaft, 15-oxidant solution, 16-cooling bath, 17-cleaning water bath, 18-drying device, 19-carbon nano tube/conductive polymer composite fiber and 20-collecting device.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
An aspect of an embodiment of the present invention provides a continuous preparation method of a carbon nanotube/conductive polymer composite fiber, including:
a floating catalytic CVD method is adopted to enable a carbon source to generate carbon nano tube aerogel through catalytic growth reaction;
the carbon nanotube aerogel is contacted with an aqueous solution of a conductive polymer monomer, so that the conductive polymer monomer uniformly permeates into a carbon nanotube gap, and simultaneously the carbon nanotube aerogel is contracted under the action of solution surface tension to prepare a carbon nanotube/conductive polymer monomer composite fiber;
under the action of an oxidant, the conductive polymer monomer in the carbon nano tube/conductive polymer monomer composite fiber is subjected to an oxidative polymerization reaction to generate a conductive polymer, so that the carbon nano tube/conductive polymer composite fiber is obtained.
In some more specific embodiments, the continuous production process comprises:
carbon source and catalyst are input into a reaction chamber of a floating catalytic CVD method along with carrier gas, and catalytic growth reaction is carried out at 1100-1300 ℃ to generate carbon nano tube aerogel.
Further, the carbon source is a liquid carbon source, particularly preferably ethanol, and is not limited thereto.
Further, the catalyst is a composite system of ferrocene and thiophene, and is not limited thereto.
In some more specific embodiments, the conductive polymer monomer includes any one of pyrrole and aniline, and is not limited thereto.
Further, the concentration of the conductive polymer monomer aqueous solution is 0.1-0.5mol/L.
In some more specific embodiments, the continuous production process comprises: and immersing the carbon nano tube/conductive polymer monomer composite fiber in an oxidant aqueous solution, and carrying out an oxidative polymerization reaction at 0-5 ℃ to obtain the carbon nano tube/conductive polymer composite fiber.
Further, the oxidant comprises iron p-toluenesulfonate, ammonium persulfate, ferric chloride, ozone and H 2 O 2 Any one or a combination of two or more of them, and is not limited thereto.
Further, the continuous preparation method further comprises: after the completion of the oxidative polymerization, the obtained reaction product is subjected to washing and drying treatment.
Another aspect of embodiments of the present invention also provides a carbon nanotube/conductive polymer composite fiber prepared by the foregoing method.
Further, the conductivity of the carbon nano tube/conductive polymer composite fiber is 5 multiplied by 10 to 7 multiplied by 10 5 S/m。
Further, the carbon nanotube/conductive polymer composite fiber includes: and uniformly filling conductive polymers distributed in gaps among the plurality of carbon nanotubes contained in the carbon nanotube fibers.
Another aspect of an embodiment of the present invention also provides a continuous preparation system of a carbon nanotube/conductive polymer composite fiber, including:
the carbon nano tube aerogel preparation device at least comprises a reaction chamber, at least is used for enabling a carbon source and a catalyst to catalyze a growth reaction to generate carbon nano tube aerogel;
the fiber preparation device is at least used for enabling the carbon nano tube aerogel to be in contact with the conductive polymer monomer aqueous solution and performing liquid-induced shrinkage to prepare the carbon nano tube/conductive polymer monomer composite fiber;
the polymerization device is at least used for enabling the conductive polymer monomer in the carbon nano tube/conductive polymer monomer composite fiber to generate a conductive polymer through oxidation polymerization reaction, so as to obtain the carbon nano tube/conductive polymer composite fiber; the method comprises the steps of,
and the collecting device is at least used for collecting the generated carbon nano tube/conductive polymer composite fiber.
In some more specific embodiments, the carbon nanotube aerogel production apparatus includes a carbon source input device, a carrier gas input device, and a reaction chamber, both of which are in communication with the reaction chamber.
Further, the reaction chamber is derived from a high temperature reaction furnace.
In some more specific embodiments, the fiber preparation device comprises an elbow having an opening at each end, and a fiber guide shaft is further disposed within the elbow.
Further, the opening is in a horn shape.
In some more specific embodiments, the polymerization apparatus further comprises a cooling unit for cooling at least the system of the oxidative polymerization reaction.
Further, the continuous preparation system further comprises a washing device and a drying device.
Further, the monomer permeation device comprises an elbow filled with pyrrole aqueous solution and a fiber guiding shaft arranged in the elbow, and one end of the elbow matched with the synthesis reaction device is in a flaring shape.
In some more specific embodiments, the polymerization unit comprises a polymerization reaction device and a cooling device.
Further, the polymerization unit further comprises a washing device and a drying device.
In some more specific embodiments, the system for continuously preparing the carbon nano tube/polypyrrole composite fiber specifically comprises a floating catalytic carbon nano tube fiber growth system, a monomer permeation device, a polymerization reaction device, a water washing device, a fiber drying device and a winding collecting system, wherein the carbon nano tube fiber growth system further comprises a raw material injection system, a sealed high-temperature tube furnace and a water sealing system with a tail gas exhaust device.
The preparation of the carbon nano tube/polypyrrole composite fiber has the following two advantages: (1) The invention is based on the introduction of conductive polymer monomer, the carbon nanotube aerogel intermediate product produced has very large carbon nanotube interval, this carbon nanotube aerogel can utilize liquid surface tension to realize the densification of liquid to form the fibrous product, the invention adopts pyrrole monomer aqueous solution to carry on this liquid densification process, in this course, pyrrole monomer can enter the interval between the tubes of the carbon nanotube aerogel product along with solution (interval is still relatively large at this moment), under the tension of solution, the interval is reduced gradually, and pyrrole monomer can remain in interval until the fibrous formation, therefore, the carbon nanotube/pyrrole composite fiber that the invention prepares has and distributes relatively even pyrrole monomer inside, and the prior art adopts the method of prefabricating carbon nanotube fiber to soak monomer solution, monomer can only enter the interval of relatively large size, the monomer distribution of fibrous inside is uneven, and the required time is relatively long, finally, the uniformity of the carbon nanotube/polypyrrole composite fiber prepared by the invention will be superior to the composite fiber prepared by the prior art too; (2) The invention designs and introduces a set of on-line polymerization, cleaning, drying and winding device, and completes the oxidative polymerization of pyrrole monomer, the removal of residual monomer and impurity after polymerization, and the drying and winding collection of fiber in the fiber collection process on the basis of preparing the carbon nano tube/pyrrole composite fiber by a floating catalytic CVD method, thereby realizing continuous and uninterrupted preparation of the carbon nano tube/polypyrrole composite fiber from raw material input to the collection of the final composite fiber, and the preparation efficiency is obviously superior to that of the stepwise preparation method adopted in the prior art.
The technical scheme of the present invention is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present invention, and detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1
Referring to fig. 1, a system for continuously preparing carbon nanotube/polypyrrole composite fiber based on a floating catalyst CVD method according to an exemplary embodiment of the present invention includes a carbon nanotube aerogel preparation device, a fiber preparation device, a polymerization device, and a collection device. The carbon nano tube aerogel preparation device comprises a reaction raw material injection device, a carrier gas input device, a furnace tube sealing flange, a high-temperature reaction furnace tube and a high-temperature furnace, wherein the fiber preparation device comprises a water seal device and a monomer permeation device, the water seal device is arranged between the synthesis reaction device and the polymerization device and is in sealing fit with the synthesis reaction device, and the monomer permeation device is arranged in the water seal device; the monomer permeation device comprises an elbow pipe with openings at two ends for containing pyrrole aqueous solution and a fiber guide shaft arranged in the elbow pipe, and one end of the elbow pipe matched with the synthesis reaction device is in a horn shape; the polymerization device comprises a polymerization reaction device, a cooling unit, a washing device and a drying device; the collecting device is a fiber winding collecting device.
Specifically, referring to fig. 1, a reaction raw material injection device 1 injects a liquid carbon source/catalyst solution into a sealed reaction furnace body through a sealing flange 3, under the action of high temperature of the furnace body, the reaction raw material is gasified and decomposed to generate an active reactant, under the action of carrier gas flow input by a carrier gas input device 2, the active reactant enters a high temperature region of a high temperature reaction furnace tube 4, the active reactant undergoes a catalytic growth reaction in the high temperature region to generate carbon nanotube aerogel 6, meanwhile, tail gas 8 is discharged through a pipeline in a water seal box 7, when passing through the liquid surface of a conductive polymer monomer aqueous solution 13 stored in an elbow 12, the carbon nanotube aerogel 6 is contracted to generate carbon nanotube/conductive polymer monomer composite fibers 11 under the action of solution surface tension, in the process, conductive polymer monomers in the solution uniformly permeate into a carbon nanotube gap, and the solution consumption can be controlled by adopting the design of solution storage of the elbow 12, so that solution loss is reduced; under the action of the fiber guiding shaft 14, the carbon nanotube/pyrrole composite fiber 11 is introduced into an oxidant solution 15, under the action of the oxidant, the conductive polymer monomer is subjected to oxidation polymerization reaction to generate conductive polymer, the reaction temperature in the oxidant solution 15 is controlled by a cooling bath 16 to control the polymerization reaction speed, the reacted fiber is introduced into a cleaning water bath 17 to remove unreacted monomer and other impurities in the fiber, and then the fiber is introduced into a fiber drying device 18 to be subjected to drying treatment, and finally the carbon nanotube/conductive polymer composite fiber 19 is obtained and is wound and collected by a fiber winding and collecting device 20.
Example 2
Utilizing the system for continuously preparing carbon nano tube/polypyrrole composite fiber based on the floating catalytic CVD method in the embodiment 1, continuously conveying ethanol/ferrocene/thiophene into a synthesis reaction device for reaction to form carbon nano tube aerogel, conveying the carbon nano tube aerogel into a pyrrole aqueous solution with the concentration of 0.44mol/L for liquid-induced shrinkage treatment at room temperature to prepare the carbon nano tube/pyrrole composite fiber, conveying the prepared carbon nano tube/pyrrole composite fiber into a p-toluenesulfonic acid aqueous solution with the concentration of 0.023mol/L for oxidation polymerization reaction at the temperature of 0 ℃, and washing, drying and collecting to prepare the continuous carbon nano tube/polypyrrole composite fiber.
Characterization of the properties:
fig. 2 is a photograph of the carbon nanotube aerogel grown by the apparatus described in example 1 in example 2, showing the carbon nanotube aerogel in a water-sealed case, and showing that the carbon nanotube aerogel is uniform and clean, and showing that the gaps between the carbon nanotubes are larger in a semitransparent state.
FIG. 3a is an SEM image of a carbon nanotube fiber, showing that there are a large number of nanoscale and submicron scale gaps/holes within the fiber that significantly increase the interfacial resistance between tubes; fig. 3b is an SEM image of the carbon nanotube/polypyrrole composite fiber prepared in example 2, and it can be seen that the aggregation and uneven distribution of polypyrrole do not occur in the composite fiber, and that the gaps/holes existing in the pure carbon nanotube fiber are greatly reduced, and the gaps/holes are filled with conductive polypyrrole, so that the microstructure is beneficial to reducing the interfacial resistance between the tubes.
FIG. 4a is a SEM image of the surface of a carbon nanotube/polypyrrole composite fiber of example 2; FIG. 4c is an EDS distribution diagram of N element on the surface of the carbon nanotube/polypyrrole composite fiber in example 2; FIG. 4b is an SEM image of the interior of the carbon nanotube/polypyrrole composite fiber of example 2; FIG. 4d is the EDS distribution diagram of N element corresponding to the inside of the carbon nanotube/polypyrrole composite fiber in example 2;
and (3) performing imaging analysis of polypyrrole characteristic elements (N elements) by adopting X-ray energy spectrum analysis (EDS) carried by a scanning electron microscope, and verifying the distribution characteristics of polypyrrole in the carbon nanotube fiber. FIGS. 4c-4d are N element distribution diagrams of the surface and interior of a composite fiber (torn open fiber surface layer), respectively, showing that the surface and interior of the fiber have a large number of uniformly distributed N atoms, and the N atom content (10%) is much higher than that of an uncomplexed pure carbon nanotube fiber (2%), indicating that polypyrrole is uniformly distributed in the interior and surface of the fiber, and conductivity measurements of the two fibers indicate that the conductivity of the carbon nanotube/polypyrrole composite fiber (5.75X10) 5 S/m) conductivity of purer carbon nanotube fiber (2.75X10) 5 S/m) was increased by 110%.
By contrast, after the uncomplexed prefabricated pure carbon nanotube fiber is dried, the carbon nanotube fiber is soaked in an aqueous solution of pyrrole monomer of 0.44mol/L for 10min at room temperature to permeate the pyrrole monomer, then an aqueous solution of p-toluenesulfonic acid with the volume of 2 times that of the pyrrole monomer solution and the concentration of 0.023mol/L is added into the same container, the mixture is kept stand for 0.5h in a refrigerator at the temperature of 0 ℃ to carry out polymerization reaction, the carbon nanotube fiber is taken out, soaked in deionized water to be washed for 10min (repeated three times), and the fiber is taken out to be dried in an oven at the temperature of 60 ℃ for 2h. The electrical conductivity of the prepared composite fiber was measured to be 3.62X10 5 S/m, conductivity of the uncomplexed carbon nanotube fiber (2.75X10 5 S/m) increased by 32% below the conductivity of the carbon nanotube/polypyrrole composite fiber of example 2.
Example 3
Utilizing the system for continuously preparing the carbon nano tube/polypyrrole composite fiber based on the floating catalytic CVD method in the embodiment 1, continuously conveying ethanol/ferrocene/thiophene into a synthesis reaction device for reaction to form carbon nano tube aerogel, conveying the carbon nano tube aerogel into 0.3mol/L aniline aqueous solution for liquid-induced shrinkage treatment at room temperature to prepare the carbon nano tube/aniline composite fiber, conveying the prepared carbon nano tube/aniline composite fiber into 0.5mol/L ammonium persulfate aqueous solution for oxidation polymerization reaction at 0 ℃, and then washing, drying and collecting to prepare the continuous carbon nano tube/polyaniline composite fiber.
Example 4
Utilizing the system for continuously preparing carbon nano tube/polypyrrole composite fiber based on the floating catalytic CVD method in the embodiment 1, continuously conveying ethanol/ferrocene/thiophene into a synthesis reaction device for reaction to form carbon nano tube aerogel, conveying the carbon nano tube aerogel into a pyrrole aqueous solution with the concentration of 0.1mol/L for liquid-induced shrinkage treatment at room temperature to prepare the carbon nano tube/pyrrole composite fiber, conveying the prepared carbon nano tube/pyrrole composite fiber into a chloride aqueous solution with the concentration of 0.2mol/L for oxidation polymerization reaction at the temperature of 5 ℃ for 10min, and then washing, drying and collecting the carbon nano tube/polypyrrole composite fiber to prepare the continuous carbon nano tube/polypyrrole composite fiber.
Example 5
Utilizing the system for continuously preparing carbon nano tube/polypyrrole composite fiber based on floating catalytic CVD method described in example 1, continuously conveying ethanol/ferrocene/thiophene into a synthesis reaction device to react to form carbon nano tube aerogel, conveying the carbon nano tube aerogel into a pyrrole aqueous solution with the concentration of 0.5mol/L to perform liquid-induced shrinkage treatment at room temperature to prepare the carbon nano tube/pyrrole composite fiber, and conveying the prepared carbon nano tube/pyrrole composite fiber into H with the concentration of 0.3mol/L 2 O 2 And (3) carrying out an oxidative polymerization reaction in the aqueous solution at the temperature of 3 ℃, and then washing, drying and collecting the aqueous solution to obtain the continuous carbon nano tube/polypyrrole composite fiber. In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (8)

1. A continuous preparation method of carbon nano tube/conductive polymer composite fiber, which is characterized by comprising the following steps:
a floating catalytic CVD method is adopted to enable a carbon source to generate carbon nano tube aerogel through catalytic growth reaction;
the carbon nanotube aerogel is contacted with the aqueous solution of the conductive polymer monomer, so that the conductive polymer monomer uniformly permeates into a carbon nanotube gap, and simultaneously the carbon nanotube aerogel is contracted under the action of solution surface tension to prepare the carbon nanotube/conductive polymer monomer composite fiber; wherein the conductive polymer monomer is selected from pyrrole; the concentration of the conductive polymer monomer aqueous solution is 0.1-0.5 mol/L;
immersing the carbon nano tube/conductive polymer monomer composite fiber in an oxidant aqueous solution, and carrying out an oxidative polymerization reaction at 0-5 ℃ to obtain the carbon nano tube/conductive polymer composite fiber.
2. The continuous preparation method according to claim 1, characterized by comprising in particular:
inputting a carbon source and a catalyst into a reaction chamber of a floating catalytic CVD method along with carrier gas, and generating carbon nano tube aerogel through catalytic growth reaction at 1100-1300 ℃; wherein the carbon source is ethanol; the catalyst is a composite system catalyst of ferrocene and thiophene.
3. The continuous production method according to claim 1, characterized in that: the oxidant is selected from the group consisting of iron p-toluenesulfonate, ammonium persulfate, ferric chloride, ozone and H 2 O 2 Any one or a combination of two or more of them.
4. The continuous production method according to claim 1, characterized by further comprising: after the completion of the oxidative polymerization, the obtained reaction product is subjected to washing and drying treatment.
5. The continuous production method according to any one of claims 1 to 4, wherein the continuous production system for producing the carbon nanotube/conductive polymer composite fiber by applying the continuous production method for carbon nanotube/conductive polymer composite fiber comprises:
the carbon nano tube aerogel preparation device at least comprises a reaction chamber, at least is used for enabling a carbon source and a catalyst to catalyze a growth reaction to generate carbon nano tube aerogel;
the fiber preparation device is at least used for enabling the carbon nano tube aerogel to be in contact with the conductive polymer monomer aqueous solution and performing liquid-induced shrinkage to prepare the carbon nano tube/conductive polymer monomer composite fiber; the fiber preparation device comprises an elbow with two open ends, and a fiber guide shaft is arranged in the elbow; the opening is in a horn shape;
the polymerization device is at least used for enabling the conductive polymer monomer in the carbon nano tube/conductive polymer monomer composite fiber to generate conductive polymer through oxidation polymerization reaction, so as to obtain the carbon nano tube/conductive polymer composite fiber; the method comprises the steps of,
and the collecting device is at least used for collecting the generated carbon nano tube/conductive polymer composite fiber.
6. The continuous production method according to claim 5, characterized in that: the carbon nano tube aerogel preparation device comprises a carbon source input device, a carrier gas input device and a reaction chamber, wherein the carbon source input device and the carrier gas input device are communicated with the reaction chamber; the reaction chamber is derived from a high temperature reaction furnace.
7. The continuous production method according to claim 5, characterized in that: the polymerization device also comprises a cooling unit which is at least used for cooling the system of the oxidative polymerization reaction.
8. The continuous production method according to claim 5, characterized in that: the continuous preparation system further comprises a washing device and a drying device.
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