KR101406646B1 - Fabrication method of multidimensional conducting polymer nanotubes via vapor deposition polymerization - Google Patents

Abstract

The present invention relates to a method for producing a multidimensional conductive polymer nanotube, wherein a polymer nanotemplate is used as a core, and a predetermined amount of a conductive polymer monomer is put in an evaporator to cause polymerization on the surface of the nanotemplate according to a predetermined time, There is provided a method for producing a multidimensional conductive polymer nanotube by growing various conductive polymer nanostructures and then removing the core.
According to the present invention, there is an advantage that a large amount of multi-dimensional conductive polymer nanotubes can be manufactured using a simple and inexpensive process. In addition, the multi-dimensional conductive polymer nanotubes grown in the nano needle shape that can be prepared in the present invention have a surface area twice as high as that of conventional conductive polymer nanotubes having smooth surface. From the viewpoint of the process, it is advantageous to manufacture a multidimensional conductive polymer nanotube having a maximized surface area by controlling temperature and pressure with a simple process.

Description

TECHNICAL FIELD [0001] The present invention relates to a multidimensional conducting polymer nanotube,

The present invention relates to a method for preparing a polymer nanotemplate by introducing an initiator into the surface of a polymer nanotemplate prepared by an electrospinning method and vapor deposition polymerization of the monomer at an appropriate temperature and time, The present invention relates to a method for producing a multidimensional conductive polymer nanotube using a method of polymerizing a conductive polymer on a surface of a nanotemplate. The nanotemplate has various shapes (nanowire and nanonodule ) Conductive polymer, and then removing the core nanotemplate, thereby easily producing a large number of multidimensional conductive polymer nanotubes.

Nanomaterials are defined as materials with a size of 1 to 100 nanometers and have excellent physical properties with a larger surface area than conventional bulk materials. Due to such a large surface area, performance has been improved in various fields such as energy and environment. However, the increase of the limited surface area shows the limit of the performance improvement. In order to overcome these disadvantages, researches on nanocomposites, surface engineering, and growth on the surface have been recently conducted It is actively proceeding.

One-dimensional electron nanomaterials, whose shape and size are controlled, are attracting attention in various fields such as transistors, lasers, light emitting diodes, solar cells, and sensors. Particularly, in the nanometer (nm) size, the one-dimensional structure can smooth the charge flow along the direction of the long axis, thereby improving the performance of the electronic device. Due to the advantages of such a one-dimensional nanostructure, methods for manufacturing one-dimensional nanostructures having various structures have been studied. In particular, metal and ceramic nanostructures can be extensively used in nanometer-sized or smaller atomic-size units using chemical vapor deposition and colloidal synthesis methods, And a manufacturing method for controlling the structure has been developed. In addition, various methods for producing inorganic nanostructures having a specific structure have been studied. However, a method of manufacturing a one-dimensional nanostructure having various structures in a polymer nanostructure has been relatively slow. Polymers consist of covalent bonds that are directly and thermally stable, and these structures have unstable structural defects in nanometer size. Due to these drawbacks, it is not easy to study the surface of a one-dimensional polymer nanostructure.

One-dimensional conductive polymer nanomaterials have been used as excellent signal-sensing devices and as transducers for various electrical devices. Particularly, it is attracting attention as a transducer of high efficiency chemical / biosensor in the sensitive device. However, their limited surface area at the nanometer still has many limitations in improving the performance of electronic devices.

The method of coating the conductive polymer on the surface of the template is a method of preparing the conductive polymer nanostructure by vapor deposition of the polymer monomer in the laboratory (Publication No. 2010-0059100, 2010-0072412) No controlled studies were conducted.

Therefore, in order to manufacture a one-dimensional conductive polymer nanostructure having a maximized surface area, a simple and safe process for controlling the growth of a specific shape of the conductive polymer on the surface of the template is strongly demanded.

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art by providing a method of polymerizing a conductive polymer monomer on a surface of a polymer nanotemplate formed through electrospinning by vapor phase polymerization and controlling a predetermined time and temperature to form various conductive polymer nanostructures To produce multidimensional conductive polymer nanotubes.

After many experiments and intensive researches, the inventors of the present invention have succeeded in producing a nanotemplate by electrospinning, adsorbing a cationic oxidizing agent, which is an initiator on the surface of the nanotemplate, and then conducting a vapor deposition , And it is confirmed that the conductive polymer nanotubes having a multidimensional structure can be manufactured by inducing the growth of conductive polymer nanostructures having various shapes (projections and needles) on the surface by controlling the predetermined time and temperature. And led to the present invention.

The present invention relates to a method of coating polypyrrole, poly (3,4-ethylenedioxythiophene), and polythiophene using a vapor deposition polymerization proceeding on the surface of a nanotemplate having a nanometer size, The surface of which is formed by a projection or a needle-like shape.

A method of manufacturing a multi-dimensional conductive polymer nanotube according to the present invention includes:

(A) preparing a polymer nanotemplate having a one-dimensional structure through electrospinning; And

(B) adsorbing a cationic oxidant, which is an initiator, on the nanotemplate surface; And

(C) introducing the nanotemplate onto which the cation oxidant is adsorbed into a vaporizer, injecting a monomer, and forming a multidimensional structure conductive polymer according to a predetermined time and temperature; And

(D) preparing a multidimensional conductive polymer nanotube by removing the nanotemplate as a core part by adding the obtained reaction material into a solvent.

The multidimensional conductive polymer nanotubes according to the present invention can be produced by a method of growing a nanostructure of conductive polymers in various shapes on the surface of a conductive polymer coated on the nanotemplate surface by controlling the time and temperature of vapor deposition polymerization As a new method, there is provided a method of growing a conductive polymer on a surface that could not be grown on the surface in the conventional method, and it is advantageous in that it is economically cheap and mass-producible to produce a polymer nanotemplate through electrospinning. In addition, it is a simple process to manufacture a conductive polymer nanotube having a maximized surface area by removing the core nanotemplate through a simple process after polymerizing the monomer through vapor deposition based on the controlled time and temperature, Unlike the manufacturing method, it is possible to manufacture nanotubes grown with various shapes of conductive polymer by a very easy method.

FIG. 1 is a scanning electron microscope (SEM) photograph of the conductive polymer nanotubes grown in the nano needle shape prepared in Examples 1, 2, 3 and 4 of the present invention.
FIG. 2 is a scanning electron microscope (SEM) photograph of the nanoparticle-grown conductive polymer nanotubes prepared in Examples 5, 6, 7 and 8 of the present invention.
3 is a scanning electron microscope (SEM) photograph of a conductive polymer nanotube having a smooth surface prepared in Example 9 of the present invention.

The polymer nanotemplate used in step (A) is not particularly limited, and any polymer capable of easily adsorbing a cationic oxidant is possible. Particularly, polymers such as polyvinyl alcohol (PVA) and poly (methyl methacrylate) (PMMA) are preferable. The diameter of the polymer nanotubes through electrospinning is not particularly limited, and is preferably 50-100 nanometers (nm). The shape is not limited to a specific shape, but a one-dimensional shape of a rod shape is preferable.

The added amount of the polymer is suitably 5 to 10 parts by weight based on 100 parts by weight of the solvent.

Step when adsorbing a cationic oxidizing agent initiator to the surface of the prepared polymer nano-templates in (B), by the cationic oxidizing agent type may be selected appropriately according to the surface of the template, in particular, iron chloride (III) (FeCl _3), A substance capable of simultaneously performing a metal salt and an oxidizing agent such as iron chloride (III) hydrate (FeCl ₃ (H ₂ O) ₆ ) and iron sulfate (III) (Fe ₂ (SO ₄ ) ₃ ) Is preferably used.

The metal salt and the oxidizing agent solution are preferably 1 to 10 parts by weight based on 100 parts by weight of the solvent. If the amount of the oxidizing agent used is less than 1 part by weight, the conductive polymer is not polymerized, and if the amount of the oxidizing agent is more than 10 parts by weight, the conductive polymer may be aggregated upon coating.

In step (C), the nanotemplate on which the cation oxidizer is adsorbed is placed in an evaporator, and a conductive polymer monomer is charged to form a multidimensional structure conductive polymer.

The vacuum of the evaporator is not particularly limited, but is preferably 760 to 1 Torr.

The temperature of the evaporator is preferably in the range of 60 ° C to 90 ° C, and when the temperature is lower than 60 ° C, the conductive polymer does not polymerize, and when the temperature is higher than 90 ° C, the polymer does not grow on the surface of the conductive polymer.

The reaction time of the evaporator is preferably from 1 hour to 6 hours. When the time is less than 1 hour, polymerization does not take place over the entire surface of the nanotemplate. If the polymerization time is more than 6 hours, polymerization occurs between the nanotemplate fibers to cause conductive polymer growth I never do that.

The conductive polymer monomer may be used regardless of the kind thereof if it is polymerized by a cation oxidizing agent. Specific examples of such monomers include pyrrole and 3,4-ethylenedioxythiophene.

The amount of addition of the conductive polymer monomer may be added in a weight ratio of 1/100 to 5 times the weight of the nanotemplate, but is not limited to these ranges and may be more or less than the above range.

In step (D), the solvent for dissolving the nanotemplate, which is the core of the polymerized multidimensional conductive polymer nanostructure, may be various. However, it is difficult to dissolve the prepared nanotemplate easily and to dissolve the conductive polymer in a suitable solvent Is preferably used. For example, it is preferable to use an aqueous solution of a polyvinyl alcohol nanotemplate and a solution of polymethylmethacrylate in dimethylformamide.

The multi-dimensional conductive polymer nanotubes can be dried by various methods, but it is preferable to dry them at room temperature and atmospheric pressure, if possible, in order to prevent aggregation of the prepared nanotubes. However, the present invention is not limited to this, and appropriate methods can be used depending on the humidity and temperature of the laboratory, the type of the solvent used, and the like.

[Example]

Hereinafter, specific examples of the present invention will be described with reference to examples, but the scope of the present invention is not limited thereto.

[Example 1]

After dissolving 5 g of polyvinyl alcohol in 100 mL of distilled water, it was connected to a commonly known electrospinning apparatus and irradiated for 30 minutes on a collecting plate formed of polyglycerol under the predetermined irradiation condition (voltage 120 KV, radiation distance 20 - 30 cm) To produce a polymer nanotemplate. The prepared nanotemplate is placed in an aqueous solution of a cationic oxidant prepared by dissolving 8 g of FeCl ₃ per 100 g of methanol for 1 minute. In order to dry the polymer nanotemplate adsorbed on the cation oxidizer, the dried nanotemplate was placed in a 60 ° C. drying oven for 3 hours, and then the dried nanotemplate was put into a vaporizer. 5 mL of polypyrrole was added thereto, Lt; / RTI > After completion of the polymerization, the reaction product was collected, and the reactant was added to 1000 mL of distilled water to remove the core nanotemplate, followed by drying at room temperature to recover the multidimensional conductive polymer nanotubes.

The multidimensional conductive polymer nanotubes were analyzed by using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and the surface of the conductive polymer nanotubes was grown on the surface (Fig. 1d). In addition, to ensure the removal of nano-template performed well core whether infrared spectroscopy (FT-IR) results to see out through the device, -OH peak of the polyvinyl alcohol is 3200 cm ^- viewed as not being observed in the ^first successfully core Was removed.

[Example 2]

Similarly to Example 1, the prepared nanotemplate was placed in an aqueous solution of a cationic oxidant prepared by dissolving 5 g of FeCl ₃ per 100 g of methanol for 1 minute, followed by vapor deposition polymerization and core removal.

The multidimensional conductive polymer nanotubes were analyzed by using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and the surface of the conductive polymer nanotubes was grown on the surface (Fig. 1a).

[Example 3]

Similarly to Example 1, the prepared nanotemplate was placed in an aqueous solution of a cationic oxidant prepared by dissolving 6 g of FeCl ₃ per 100 g of methanol for 1 minute, followed by vapor deposition polymerization and core removal.

The multidimensional conductive polymer nanotubes were analyzed by using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and the surface of the conductive polymer nanotubes was grown on the surface (Figure 1b).

[Example 4]

Similar to Example 1, the prepared nanotemplate was placed in an aqueous solution of a cationic oxidant prepared by dissolving 7 g of FeCl ₃ per 100 g of methanol for 1 minute, followed by vapor deposition polymerization and core removal.

The multidimensional conductive polymer nanotubes were analyzed by using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and the surface of the conductive polymer nanotubes was grown on the surface (Figure 1c).

[Example 5]

The prepared nanotemplate was put in an aqueous solution of a cationic oxidant prepared by dissolving 8 g of FeCl ₃ per 100 g of methanol for 1 minute and then the nanotemplate adsorbed on the prepared cation oxidant was placed in a vaporizer at a temperature of 90 ° C , And 760 Torr, the core removal was completed.

The multidimensional conductive polymer nanotubes prepared were analyzed using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and had conductive polymer protrusions grown on the surface thereof 2d).

[Example 6]

Similarly to Example 1, the prepared nanotemplate was immersed in an aqueous solution of a cationic oxidant prepared by dissolving 5 g of FeCl ₃ relative to 100 g of methanol for 1 minute, and then the nanotemplate adsorbed on the prepared cation oxidant was placed in a vaporizer at 90 ° C , And 760 Torr, the core removal was completed.

The multidimensional conductive polymer nanotubes prepared were analyzed using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and had conductive polymer protrusions grown on the surface thereof 2a).

[Example 7]

Similarly to Example 1, the prepared nanotemplate was immersed in an aqueous solution of a cationic oxidant prepared by dissolving 6 g of FeCl ₃ per 100 g of methanol for 1 minute, and then the nanotemplate adsorbed on the prepared cation oxidant was placed in a vaporizer at 90 ° C , And 760 Torr, the core removal was completed.

The multidimensional conductive polymer nanotubes prepared were analyzed using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and had conductive polymer protrusions grown on the surface thereof 2b).

[Example 8]

The prepared nanotemplate was put in an aqueous solution of a cationic oxidant prepared by dissolving 7 g of FeCl ₃ per 100 g of methanol for 1 minute and then the prepared nanotemplate adsorbed on the cation oxidant was placed in a vaporizer at a temperature of 90 ° C , And 760 Torr, the core removal was completed.

The multidimensional conductive polymer nanotubes prepared were analyzed using a scanning electron microscope (SEM). As a result, it was confirmed that the multimodal conductive polymer nanotubes had a thickness of about 100 nm and had conductive polymer protrusions grown on the surface thereof 2c).

[Example 9]

As a control experiment, the prepared nanotemplate was placed in an aqueous solution of a cationic oxidant prepared by dissolving 8 g of FeCl ₃ per 100 g of methanol, for 1 minute, and the nanotemplate adsorbed on the prepared cation oxidant was applied to an evaporator And polymerization was completed under the conditions of a temperature of 90 DEG C and a pressure of 1 Torr, and then the core removal was completed.

The prepared multi-dimensional conductive polymer nanotubes were analyzed using a transmission electron microscope (TEM). As a result, it was confirmed that the polymer nanotubes were conductive polymer nanotubes having a thickness of about 100 nm and a smooth surface (FIG. 3).

[Example 10]

The surface areas of the nanostructures prepared in Examples 1, 5 and 9 were calculated. As a result, the conductive polymer nanotubes (62 m ² g ^-1 ) grown with nano-nano-structured structure, the conductive polymer nanotubes (48 m ² g ^-1 ) grown with the nano-prism structure, the conductive polymer nanotubes 31 m ² g ^-1 ), it was confirmed that the surface area increased about twice.

Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

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Claims (7)

Preparing a polymer nanotemplate having a one-dimensional structure by electrospinning; And
Adsorbing a cationic oxidant as an initiator on the nanotemplate surface; And
Introducing the nanotemplate adsorbed with the cation oxidizer into a vaporizer to introduce a monomer, and forming a multidimensional structure conductive polymer according to a predetermined time and temperature; And
The method for preparing a multidimensional conductive polymer nanotubes by removing the nanotemplate as a core part by adding the obtained reaction material into a solvent. The method according to claim 1, wherein the polymer nanotemplate is polyvinyl alcohol or polymethylmethacrylate. Of claim 1, wherein the cationic oxidizing agent is iron (III) chloride (FeCl _3), iron (III) chloride hydrate _{(FeCl 3 (H 2 O)} 6), iron sulfate _{(III) (Fe 2 (SO} 4) 3) Wherein the conductive polymer nanotubes have a thickness of 100 nm or less. The method of claim 1, wherein the monomer to be added to the evaporator is one of pyrrole and 3,4-ethylenedioxythiophene. The method according to claim 1, wherein the reaction temperature of the evaporator is in a range of 60 ° C to 90 ° C. The method of manufacturing a multi-dimensional conductive polymer nanotube according to claim 1, wherein the atmospheric pressure in the evaporator is 1 Torr - 760 Torr. The method of claim 1, wherein the time for forming the conductive polymer is from 1 hour to 6 hours.




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