KR101687396B1 - Preparation method of conductive polymer nano-marterial - Google Patents

Abstract

The present invention provides a method for producing a semiconductor device, comprising: adding a dopant to a mixed solvent containing water and an organic solvent in a volume ratio of 5: 1 to 0.5: 1; And adding a monomer, an initiator and an oxidizing agent of a conductive polymer to the mixed solvent to which the dopant is added, and polymerizing the conductive polymer nanomaterial.

Description

TECHNICAL FIELD [0001] The present invention relates to a conductive polymer nanomaterial,

The present invention relates to a method for producing a conductive polymer nanomaterial, and more particularly, to a method for mass-producing a conductive polymer nanofiber having excellent mechanical properties, high heat resistance and electrical conductivity in a short time.

A nanomaterial is a material having a function generally ranging from 1 to 100 nanometers in size. In terms of size, it may be regarded as an intermediate state between a molecule and a large lump solid. Nanomaterials have new electronic, magnetic, optical, and electrical properties that can not be seen in molecular or bulk solid state. These properties result from the quantum size effect.

In order to develop various new materials by using novel properties and physical properties of these nanomaterials, researches on nanomaterials using metals, metal oxides, inorganic materials, and organic polymer materials have been continuously carried out. As a result, Various methods for manufacturing metal and inorganic semiconductor nanoparticles have been disclosed, and various nanomaterials have been applied to a wide range of industrial fields.

However, in the case of a nanomaterial using an organic polymer, the manufacturing process is relatively complicated as compared with a nanomaterial such as a metal or an inorganic semiconductor, and its application range has been relatively limited, and commercialization has a certain limit.

In recent years, interest in nanomaterials has increased, and research into one-dimensional conductive nanostructured materials such as nanofibers or nanotubes has been actively carried out. In order to develop a one-dimensional conductive nanostructured material into electrical / electronic devices, chemical / Many researches have been made to apply to various fields such as biosensors, electromagnetic wave shielding materials, and metal corrosion inhibitors.

In particular, one-dimensional intrinsic conductive polymer nanomaterials are attracting attention as important conductive materials due to low cost of materials, various color changes depending on the degree of oxidation, and stable electrical conductivity to the external environment. Among them, 1-D Intrinsic Conducting Polymer nanomaterials have been studied extensively.

Previously, in order to prepare a 1-D intrinsic conductive polymer nanomaterial, a solution of an intrinsic conductive polymer monomer was injected into a mold such as an anodic aluminum oxide or a polycarbonate membrane, Or by electrochemical methods. However, this method has problems such as a problem of wastewater treatment and complicated process design by using a solution of strong acid, strong base or hydrogen fluoride in order to recover the reaction product obtained from the mold. As a result, There was a limit in which it was not suitable for mass production.

In order to solve such a conventional method, 1-D Intrinsic Conducting by microemulsion polymerization using an organic acid such as? -Naphthalenesulfonic acid or camphorsulfonic acid as a dopant A method for producing a polymer nanomaterial has been attempted. However, this method has limitations in mass production due to the characteristics of the emulsion polymerization method involving the step of removing the surfactant used in the polymerization, and the production cost of the final product is increased due to the complexity of the production process and the cost structure There was a problem of rising.

In addition, U.S. Patent No. 7,144,949 discloses a method for producing a 1-D intrinsic conductive polymer nanomaterial by an interfacial polymerization method in which an aniline monomer is dissolved in an organic solvent and then mixed with a dopant dispersed in an aqueous solution. However, Polymerization has a certain limit in mass production, and recently, there has been a problem in that the physical properties required in the field to which 1-D intrinsic conductive polymer nanomaterials are applied, for example, high heat resistance and electric conductivity can not be sufficiently secured.

US Patent No. 7144949

The present invention provides a method for mass production of conductive polymer nanofibers having excellent mechanical properties, high heat resistance and electrical conductivity in a short time.

In the present specification, a method is provided for adding a dopant to a mixed solvent containing water and an organic solvent in a volume ratio of 5: 1 to 0.5: 1; And adding a monomer, an initiator, and an oxidizer of a conductive polymer to the mixed solvent to which the dopant is added, and polymerizing the conductive polymer nanomaterial.

Hereinafter, a method for producing a conductive polymer nanomaterial according to a specific embodiment of the present invention will be described in detail.

As described above, according to an embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: adding a dopant to a mixed solvent containing water and an organic solvent in a volume ratio of 5: 1 to 0.5: 1; And adding a monomer, an initiator and an oxidizing agent of a conductive polymer to the mixed solvent to which the dopant is added, and polymerizing the conductive polymer nanomaterial.

The present inventors have conducted studies on conducting polymer nanomaterials and have succeeded in mass production of conductive polymer nanomaterials having high heat resistance and electrical conductivity as well as excellent physical properties in a short time by using the above specific manufacturing method Through experiments, we confirmed and completed the invention.

Specifically, after a first dopant is added to a mixed solvent containing water and an organic solvent in a volume ratio of 5: 1 to 0.5: 1, or in a volume ratio of 4: 1 to 1: 1, the monomer, initiator And an oxidizing agent are added to conduct the polymerization reaction, a conductive polymer nanomaterial having a high conductivity in a relatively short time, for example, a conductive polymer nanofiber having a diameter of 10 nm to 250 nm, or 50 nm to 200 nm is provided .

When a dopant is added to the mixed solvent in advance, it is possible to form a microemulsion. A monomer and an initiator of the conductive polymer may be added to the microemulsion to form a micelle having a hydrophobic component surrounding the hydrophilic component. Then, an initiator may be added to the solution in which the micelle is formed, and polymerization may proceed to prepare a conductive polymer nanomaterial.

The step of adding a monomer, an initiator and an oxidizer of a conductive polymer to the mixed solvent to which the dopant is added may be carried out by adding a monomer and an initiator of the conductive polymer to the mixed solvent to which the dopant has been added to form a hydrophobic component Forming a micelle; And adding an initiator to the solution in which the micelle is formed.

The microemulsion may have a more homogeneous composition by using a mixed solvent containing water and an organic solvent in a volume ratio of 5: 1 to 0.5: 1 or a volume ratio of 4: 1 to 1: 1, A micelle having a shape in which the hydrophilic component surrounds the hydrophobic component may be formed by adding a monomer of the conductive polymer and an initiator.

For example, when the volume ratio of water to organic solvent is more than 5: 1, the material used as a dopant is not mixed or precipitated to form micelles of the above-mentioned shape . When the amount of water relative to the organic solvent is too small, for example, when the volume ratio of the water to the organic solvent is less than 0.5: 1, the monomers and the initiator are not dissolved, and thus the micelle having the shape described above may not be uniformly formed .

Meanwhile, adding the dopant to the mixed solvent containing water and the organic solvent at a volume ratio of 5: 1 to 0.5: 1 may include adding 10 to 1000 g or 30 to 300 g of the dopant to 1 L of the mixed solvent . As described above, a microemulsion can be formed by adding a dopant to the mixed solvent. The microemulsion can have a more homogeneous composition by adding the above-described amount of the dopant to the volume of the mixed solvent. When the weight of the dopant in the mixed solvent is too small, it may be difficult to ensure sufficient conductivity of the conductive nanomaterial to be produced or to secure necessary mechanical properties. In addition, when the weight of the dopant in the mixed solvent is too large, more amorphous bulk material may be generated than the conductive polymer nanomaterial to be produced.

The organic solvent may include at least one selected from the group consisting of methanol, ethanol, propanol, butanol, iso-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone and cyclohexanone.

The initiator may comprise a compound comprising a functional group in which at least one amine functional group is substituted on the benzene ring. The initiator can initiate an initial polymerization step.

Specifically, the compound containing a functional group in which at least one amine functional group is substituted on the benzene ring may be one selected from the group consisting of phenylenediamine, diphenylenediamine, and 4- (4-phenyl-1-piperazinyl) The above compounds may be included.

The molar ratio of the monomer: initiator of the conductive polymer may be 1: 0.001 to 1: 1. If the amount of the initiator is too small, the initiating effect is insufficient and the above-mentioned polymerization reaction does not sufficiently take place, or it may be difficult to form the micelle in the shape of the hydrophobic component surrounded by the hydrophilic component. In addition, if the amount of the initiator is too large, the polymerization reaction proceeds too rapidly, and nanomaterial formation may be rather inhibited.

The dopant may include at least one compound selected from the group consisting of benzenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid, and polystyrene sulfonate.

In the polymerization step, the weight of the monomer of the conductive polymer in the reaction solution may be 0.005 g / mL to 0.5 g / mL, or 0.01 g / mL to 0.1 g / mL. If the weight of the monomer of the conductive polymer in the reaction solution is too small, it may be difficult to ensure sufficient conductivity of the produced conductive nanomaterial or to secure necessary mechanical properties. Also, if the weight of the monomer of the conductive polymer in the reaction solution is too high, more amorphous bulk material may be produced than the conductive polymer nanomaterial to be produced.

The monomer of the conductive polymer is selected from the group consisting of aniline, alkyl aniline having 1 to 5 carbon atoms, alkoxyaniline having 1 to 5 carbon atoms, dialkoxyaniline having 1 to 5 carbon atoms, sulfonyl aniline, nitroaniline, pyrrole, ethylenedioxythiophene (EDOT) And thiophenes. The term " a "

As described above, the oxidizing agent can act as an initiator of the polymerization reaction, and the compounds usable as the oxidizing agent are not particularly limited, but specifically include persulfates, iodates, chlorates, dichromates, metal chlorides , Peroxydisulfate salts, or mixtures thereof.

 As the persulfate, ammonium persulfate, potassium persulfate or sodium persulfate may be used. As the iodate, potassium iodate and the like can be used. As the chlorate, potassium chlorate and the like can be used. As the acid salt, potassium dichromate can be used. As the metal chloride, ferric chloride, cupric chloride, copper chloride and the like can be used. As the peroxydisulfate salt, ammonium peroxydisulfate and the like can be used .

The molar ratio of the monomer to the oxidizing agent of the conductive polymer may be 1: 0.1 to 1:10. If the amount of the oxidizing agent serving as the polymerization initiator is too small, the polymerization efficiency may be greatly reduced or the conductive polymer nanomaterial may not be sufficiently produced. If the amount of the oxidizing agent is too large, excessive polymerization may occur and unnecessary heat may be generated, or side branches may excessively bind to the main chain of the conductive polymer nanomaterial to be synthesized, which may make it difficult to secure proper shape or physical properties.

The polymerization may be carried out at from -20 캜 to 100 캜, or from 0 캜 to 30 캜.

The finally obtained conductive polymer nanomaterial can be washed with an organic solvent such as alcohol or acetone to increase its purity and can be obtained as a final product through a process such as drying.

The finally obtained conductive polymer nanomaterial can have electric conductivity of 10 ^-8 S / cm or more at room temperature and is applied as a main additive for antistatic, electrostatic dissipative, and electromagnetic interference shielding materials can do.

According to the present invention, it is possible to provide a production method capable of mass-producing a conductive polymer nanomaterial having excellent mechanical properties, high heat resistance and improved electrical conductivity in a short time, and a conductive polymer nanomaterial provided from the production method.

The provided conductive polymer nanomaterials have high heat resistance and electrical conductivity and can be applied as a main additive for antistatic, electrostatic dissipative, and electromagnetic interference shielding materials.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  1 to 7: Conductive polymer Nanomaterial  Produce]

Water and an organic solvent were mixed in the volume ratios shown in Table 1 below, 1000 g of dodecylbenzenesulfonic acid was added dropwise to the mixed solvent while stirring at 150 rpm, and the mixture was stirred.

Then, the monomer shown in Table 1 was added dropwise to the mixed solvent containing dodecylbenzenesulfonic acid added thereto, and an initiator and an oxidizing agent were added. After about 1 minute, the color of the solution was changed from colorless to dark green, After stirring for 2 hours, the reaction was terminated by pouring 3 L of ethanol. At this time, the resultant was washed once with ethanol and acetone, respectively, and dried to prepare a conductive polymer nanomaterial.

The prepared conductive polymer nanomaterials were prepared in the form of pellets having a diameter of 10 mm, and the electrical conductivity was measured by a 4-probe probe method.

Item Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Furtherance Solvent 1 Water 7L 5L water Water 7L 5L water 5L water 5L water 5L water Solvent 2 EtOH 3L EtOH 5L Acetone 3L Acetone 5L EtOH 5L EtOH 5L EtOH 5L Dopant DBSA 1000g DBSA 1000g DBSA 1000g DBSA 1000g DBSA 1000g DBSA 1000g DBSA 1000g Monomer Aniline 125g Aniline 125g Aniline 125g Aniline 125g Pyrrole 125g EDOT 125g Thiophene 125g Oxidant APS 150g APS 150g APS 150g APS 150g APS 150g APS 150g APS 150g Initiator PDA 0.4g PDA 0.4g PDA 0.4g PDA 0.4g Condition reaction
time 20 minutes 20 minutes 20 minutes 20 minutes 20 minutes 20 minutes 20 minutes reaction
Temperature 5 ^o C 5 ^o C 5 ^o C 5 ^o C 5 ^o C 5 ^o C 5 ^o C Total time 3h 3h 3h 3h 3h 3h 3h result shape
(diameter) Nanofiber
(120 nm) Nanofiber
(50 nm) Nanofiber
(75 nm) Nanofiber
(70 nm) Nanofiber
(120 nm) Nanofiber
(50 nm) Nanofiber
(100 nm) conductivity
(S / cm) 10 ¹ 10 ¹ 10 ¹ 10 ¹ 10 ² 10 ² 10 ⁰

-DBSA: Dodecylbenzenedisulfonic acid

-APS: Ammonium Persulfate

-PDA: Phenylenediamine

[ Comparative Example  1 to 3: Conductive polymer Nanomaterial  Produce]

Comparative Example  1 and 2

Conductive polymer nanomaterials were prepared in the same manner as in Example 1, except that the components listed in Table 2 were used. The prepared conductive polymer nanomaterials were prepared in the form of pellets having a diameter of 10 mm, and the electrical conductivity was measured by a 4-probe probe method.

Comparative Example  3

As shown in the following Table 2, polymer nanomaterials were prepared in the same manner as in Example 1, except that water and ethanol were used at different ratios.

Item Comparative Example 1 Comparative Example 2 Comparative Example 3 Furtherance Solvent 1 Water 10L Water 2L Solvent 2 EtOH 10 L EtOH 8L Dopant DBSA 1000g DBSA 1000g DBSA 1000g Monomer Aniline 125g Aniline 125g Aniline 125g Oxidant APS 150g APS 150g APS 150g Dispersant Initiator PDA 0.4g PDA 0.4g Condition Reaction time 20 minutes 30 minutes 20 minutes Reaction temperature 5 ^o C 5 ^o C 5 ^o C Total time 5h 5h 5h result shape Nanoparticle Amorphous Amorphous conductivity
(S / cm) 10 ¹ 10 ^-1 10 ⁰

- Ammonia sol'n: ammonia hydroxide solution 30%

As shown in Table 1, it was confirmed that the polymer nanofibers having excellent mechanical properties, high heat resistance and electrical conductivity can be produced within a relatively short time period.

On the contrary, in Comparative Examples 1 and 2 using only either water or ethanol, nanomaterials having relatively low conductivity were prepared (Comparative Examples 1 and 2), and the nanomaterials produced were amorphous (Comparative Example 2) .

Particularly, in the case of Comparative Example 3 in which ethanol was used at a volume ratio of 4 times that of water, it was confirmed that not only the conductivity was relatively low but also the shape of the produced polymer nanomaterial was amorphous.

Claims (15)

Adding a dopant to a mixed solvent containing water and an organic solvent in a volume ratio of 4: 1 to 1: 1; And
Adding a monomer of the conductive polymer, an initiator and an oxidizing agent to the mixed solvent to which the dopant is added,
The step of adding a dopant to a mixed solvent containing water and an organic solvent in a volume ratio of 4: 1 to 1: 1 may include adding 30 to 300 g of a dopant to 1 L of the mixed solvent,
Wherein the organic solvent includes at least one selected from the group consisting of methanol, ethanol, and acetone,
The step of adding the monomer of the conductive polymer, the initiator and the oxidizing agent to the mixed solvent to which the dopant is added,
Adding a monomer and an initiator of the conductive polymer to the mixed solvent to which the dopant is added to form a micelle having a hydrophilic component surrounding the hydrophilic component; And
And adding an initiator to the solution in which the micelle is formed.
delete The method according to claim 1,
Wherein the conductive polymer nanomaterial has a shape of a nanofiber having a diameter of 10 nm to 250 nm,
(Method for producing conductive polymer nanomaterial).
delete The method according to claim 1,
Wherein the initiator comprises a compound comprising a functional group in which at least one amine functional group is substituted on the benzene ring.
6. The method of claim 5,
The compound containing a functional group in which the benzene ring is substituted with at least one amine functional group may be at least one compound selected from the group consisting of phenylenediamine, diphenylenediamine and 4- (4-phenyl-1-piperazinyl) Including,
(Method for producing conductive polymer nanomaterial).
delete delete The method according to claim 1,
Wherein the dopant comprises at least one compound selected from the group consisting of benzenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, p-toluenesulfonic acid and polystyrene sulfonate.
(Method for producing conductive polymer nanomaterial).
The method according to claim 1,
The monomer of the conductive polymer is selected from the group consisting of aniline, alkyl aniline having 1 to 5 carbon atoms, alkoxyaniline having 1 to 5 carbon atoms, dialkoxyaniline having 1 to 5 carbon atoms, sulfonyl aniline, nitroaniline, pyrrole, ethylenedioxythiophene (EDOT) And at least one selected from the group consisting of a thiophene and a thiophene.
The method according to claim 1,
Wherein the oxidizing agent comprises at least one selected from the group consisting of a persulfate, an iodate, a chlorate, a dichromate, a metal chloride and a peroxydisulfate salt.
The method according to claim 1,
In the step of adding the monomer of the conductive polymer, the initiator and the oxidizing agent to the mixed solvent to which the dopant is added and polymerizing,
The weight of the monomer of the conductive polymer in the reaction solution containing the dopant-added mixed solvent, the monomer of the conductive polymer, the initiator, and the oxidizer is 0.005 g / mL to 0.5 g / mL,
(Method for producing conductive polymer nanomaterial).
The method according to claim 1,
Wherein the molar ratio of the monomer of the conductive polymer to the initiator is 1: 0.001 to 1:10.
The method according to claim 1,
Wherein the molar ratio of the monomer of the conductive polymer to the oxidant is 1: 0.1 to 1:10.
The method according to claim 1,
Wherein the polymerization is carried out at a temperature of from -20 占 폚 to 100 占 폚.