KR20150124065A - Device and manufacturing method of conductive polymer solution using the same - Google Patents

Abstract

The present invention relates to a device and a manufacturing method of a conductive polymer solution using the same, wherein the conductive polymer solution can be manufactured under injection of inert gas, thereby preventing oxidation of a conductive polymer by removing oxide produced during a producing process, being able to increase electrical conductivity and being able to reduce producing cost.

Description

And a method for manufacturing a conductive polymer solution using the same.

The present invention relates to a device and a method for producing a conductive polymer solution using the same.

BACKGROUND OF THE INVENTION [0002] As various home appliances and communication devices including computers are digitized and rapidly improved in performance, development of transparent conductive materials for use as electrodes of electronic devices is required. For example, in order to realize a portable display, the electrode material for a display must have transparency and low resistance as well as high flexibility to cope with mechanical impact, and even if the device is overheated and exposed to a high temperature, Should not be large.

ITO (indium-tin oxide) is the most commonly used transparent electrode material for displays. However, when the transparent electrode is formed of ITO, not only is an excessive cost consumed, but also it is difficult to realize a large area. In particular, when the ITO is coated on a large area, the change of the sheet resistance is large, and the luminance and luminous efficiency of the display are reduced. In addition, indium, which is the main raw material of ITO, is a limited minerals and is rapidly depleting as the display market expands.

 In order to overcome the disadvantages of ITO, studies are being conducted to form a transparent electrode using a conductive polymer having excellent flexibility and a simple coating process. However, when the transparent electrode is formed of a conductive polymer, the resistance of the conductive polymer film is increased due to unreacted ions, unreacted monomers, unreacted oligomers, and excessive polymer electrolytes after the reaction, thereby lowering the electric conductivity. For example, in order to lower the resistance of a transparent electrode formed of PEDOT: PSS, a process of washing the PEDOT: PSS film using a solvent capable of dissolving PSS such as ethylene glycol, DMSO, sulfuric acid, or an ionic electrolyte Respectively. However, such a method has a disadvantage in that the process is complicated and takes a long time, which is a limitation in application to a real industry.

In addition, when the transparent electrode is formed of a conductive polymer, the conductive polymer in which the reaction is terminated has a problem in that the reaction is terminated in a state of being not doped so as to obtain maximum conductivity, and low conductivity is exhibited. In order to solve such a problem, recently, a method has been studied in which a film is formed using a full solid polymer solution and then doped in a solution containing a dopant for further doping. This is a disadvantage in that the process is complicated and the process takes a long time . Alternatively, the doping rate of the conductive polymer can be increased by adding a dopant to the conductive polymer solution. However, when the ion dopant is added to the PEDOT: PSS solution containing a large amount of the ionic substance, the viscosity of the solution gradually increases, There is a disadvantage in that a phenomenon of falling and becoming hard with gel occurs.

As a method of synthesizing the conductive polymer having high conductivity, a vacuum process method has been performed in which the inside of the reaction vessel is lowered to a pressure lower than the atmospheric pressure by using a vacuum pump, and polymerization reaction is carried out. For example, when synthesizing PEDOT: PSS, an ionic oxidizing agent containing Fe ^{+ 3} and an ionic oxidizing agent containing persulfate are used together to cause the oxidation reaction of the EDOT monomer. At this time, sodium persulfate, which is a sodium-based oxidizing agent, and potassium persulfate, which is a potassium-based oxidizing agent, are frequently used. These oxidizing agents dissolve in water and react with water to generate oxygen as a by-product. When the polymerization is carried out under vacuum, the oxygen generated through the reaction can be removed by a pump and the polymerization reaction can be carried out. This is to prevent oxidation of PEDOT due to oxygen generated in the course of the reaction. However, when using a vacuum process, a very expensive apparatus with high strength is required because the reaction vessel must withstand the vacuum. In addition, a vacuum pump is used to realize a vacuum condition. At this time, when water vapor enters the expensive vacuum pump, the vacuum pump may fail. Further, when the polymerization reaction proceeds under vacuum, the liquid monomer and the solvent may be evaporated, resulting in a problem that the uniformity of the product is deteriorated and the physical properties are deteriorated. As described above, since the evaporation of water is not constant, it is difficult to control the concentration and the viscosity and the desired physical properties can not be obtained when the vacuum is broken.

Korean Patent Publication No. 2012-0077112

The present invention relates to a device and a method for producing a conductive polymer solution using the same, wherein the conductive polymer solution can be produced under continuous injection of an inert gas.

The present invention can provide an apparatus for producing a conductive polymer solution. As an example,

A reaction container comprising a solution containing a conductive polymer, an ion and an ionic polymer electrolyte;

And an inert gas injection unit for continuously injecting the inert gas into the solution contained in the reaction vessel for a period of time during which the reaction proceeds,

The reaction vessel may provide an apparatus wherein the average pressure during the reaction is greater than 1 atm.

In addition, the present invention can provide a method for producing a conductive polymer solution. As an example,

Continuous inert gas is injected and, under pressure conditions above 1 atm,

And a step of preparing a solution containing a conductive polymer, an ion and an ionic polymer electrolyte.

By manufacturing the conductive polymer solution through the apparatus according to the present invention, the oxygen generated during the manufacturing process can be removed to prevent the oxidation of the conductive polymer, the electric conductivity can be increased, and the manufacturing cost can be reduced.

Figures 1 to 4 are schematic diagrams of an apparatus according to the invention, respectively, in one embodiment.

The present invention relates to a device and a method for producing a conductive polymer solution using the same.

As an example of such an apparatus,

A reaction container comprising a solution containing a conductive polymer, an ion and an ionic polymer electrolyte;

And an inert gas injection unit for continuously injecting the inert gas into the solution contained in the reaction vessel for a period of time during which the reaction proceeds,

The reaction vessel may have an average pressure over 1 atm during the reaction.

Specifically, an inert gas injection unit is disposed in a reaction vessel containing a solution containing a conductive polymer, an ion, and an ionic polymer electrolyte, whereby an inert gas can be continuously injected in an intermittent or intermittent state have.

In a solution containing the conductive polymer, ion and ionic polymer electrolyte, ions can be used as a catalyst, and the ions can react with water vapor to generate oxygen as a by-product. In addition, the oxygen may cause an overoxidation reaction of the conductive polymer, thereby lowering the electrical conductivity of the conductive polymer. However, in the present invention, the inert gas injected through the inert gas injection unit may be used to remove the oxygen generated during the reaction in the reaction vessel to prevent the above problems. For example, as the purity of the inert gas injected through the inert gas injection unit is higher, the conductive polymer can be easily removed and thus a conductive polymer having a high electrical conductivity can be produced.

The inert gas is not particularly limited as long as it does not react with the solution containing the conductive polymer, the ion and the ionic polymer electrolyte. For example, at least one of nitrogen, helium, neon, argon, krypton, . ≪ / RTI > Further, it may include a mixed gas in which two or more kinds are mixed.

For example, when sodium sulfate is used as the ion, a reaction as shown in the following reaction formula 1 may be performed in the reaction vessel.

[Reaction Scheme 1]

S ₂ O ₈ ^-2 + H ₂ O → 2HSO ₄ ^-1 + 1 / 2O ₂

At this time, the generated oxygen is removed through a vacuum process using a vacuum pump, but there are many problems as described above. In the present invention, the generated oxygen may be mixed with the inert gas injected through the inert gas inlet port to dissolve and discharge the oxygen, thereby removing the oxygen in the reaction container.

For example, since an inert gas is continuously injected into the reaction vessel, the pressure in the reaction vessel can be maintained above 1 atm higher than the atmospheric pressure. Specifically, the pressure may be at least 1.2 atm. The pressure may be in the range of, for example, 1.2 atm to 1.5 atm, 1.5 to 2.0 atm, or 1.5 atm to 1.8 atm. By conducting the reaction under a pressurized condition in which the pressure in the reaction vessel is 1.2 atm or more, the reaction rate can be increased, thereby saving the processing cost.

The reaction vessel may be filled with an inert gas before the initiation of the reaction. For example, the state can be performed by injecting an inert gas into the reaction vessel before the solution containing the conductive polymer, the ion, and the ionic polymer electrolyte is received in the reaction vessel. In this way, unnecessary reaction elements that may be present inside the reaction vessel can be removed. Specifically, it is possible to produce a more pure conductive polymer solution by removing elements that may cause a decrease in the electrical conductivity of the conductive polymer.

The filtration unit may further include a filtration unit that performs filtration by supplying the reaction solution in the reaction vessel. Thus, the reaction solution in the reaction vessel can be fed to the filtration unit to perform filtration according to the molecular weight. Specifically, the filtration unit can use a filtration membrane that does not allow the conductive polymer to pass therethrough, and can filter out other components effectively. For example, the filtration membrane can allow ions in the solution to pass therethrough, and unlike the conductive polymer, it can be a filtration membrane that allows the ionic polymer electrolyte to pass through the chain. The filtration membrane may include a filtration membrane or a filtration membrane divided into pore sizes based on the molecular weight, and is not particularly limited as long as it is a filtration membrane that does not allow the conductive polymer to pass therethrough.

By using the filtration membrane, ions, unreacted monomers, unreacted oligomers, and excess polyelectrolytes other than the conductive polymer according to the present invention can be effectively removed. Through this, the electrical conductivity can be increased by lowering the resistance represented by the impurity.

The reaction vessel may further include a gas outlet.

Specifically, the oxygen generated through the reaction scheme 1 may be reacted with the inert gas and discharged through the gas outlet port to be removed.

The reaction vessel may further include a cooling circulation device.

In particular, the cooling and circulating apparatus can easily produce a conductive polymer at a proper cooling temperature and at a constant temperature, thereby controlling the reaction rate or the oxidation reaction rate. In addition, it is possible to prevent the generation of water vapor in the reaction vessel by cooling the heat generated in the mixing and reaction of the conductive polymer solution in the reaction vessel. This makes it possible to solve the problem caused by the water vapor generated in the reaction vessel.

An apparatus according to the present invention can be described with reference to Figs. 1 to 4, the reaction vessel 100, 200, 300, 400 may be a double jacketed reactor. For example, the reaction vessel includes a solution containing a conductive polymer, an ion, and an ionic polymer electrolyte in a reaction vessel 100, 200, 300, 400 equipped with an impeller (not shown) 220, 320, 420 located above the reaction vessels 100, 200, 300, 400. The inert gas injection units 110, 210, 310, And may include a cooling circulation device (130, 230, 330, 430) connected to the reaction vessel.

Here, in Figs. 1 to 4, the positions of the inert gas injection portions may be different from each other.

As one example, the inert gas injection portion may be provided at the lower portion of the reaction vessel to supply an inert gas to the solution in the reaction vessel. This can be confirmed from FIG. Specifically, it is confirmed that the inert gas injection unit 110 of FIG. 1 is installed under the reaction vessel 100 and injects an inert gas into the reaction vessel.

As another example, the inert gas injection portion may be provided at an upper portion of the reaction vessel to supply an inert gas to the solution in the reaction vessel. This can be confirmed from FIG. Specifically, it can be confirmed that the inert gas injection unit 210 of FIG. 2 is installed above the reaction vessel 200 to inject an inert gas into the reaction vessel.

As another example, the inert gas injection portion may be formed by dividing the inert gas injection portion into a plurality of injection portions on the same plane in the reaction vessel. This can be confirmed from FIG. Specifically, the inert gas injection unit 310 of FIG. 3 is divided into a plurality of injection units on the same plane of the lower part of the reaction vessel 300, so that the inert gas can uniformly be supplied to the solution in the reaction vessel.

As another example, the inert gas injection portion may be formed by dividing the inert gas injection portion into the same plurality of injection portions in a plane having different heights in the reaction vessel. This can be confirmed from FIG. Specifically, the inert gas injection unit 410 shown in FIG. 4 is formed on the side surface of the reaction vessel 400 and is divided into a plurality of injection units on a plane having different heights to uniformly supply the inert gas to the solution in the reaction vessel .

As another example, the inert gas injection portion may be formed at a position where the inert gas injection portion is immersed in the solution in the reaction vessel. Specifically, referring to Figs. 1 to 4, the inert gas injection unit may inject an inert gas at a position where the inert gas injection unit is connected to the inside of the reaction vessel and immersed from above or below the reaction vessel.

The present invention can provide a method for producing a conductive polymer solution. As an example,

Continuous inert gas injection, under pressure conditions exceeding 1 atm,

And a step of preparing a solution containing a conductive polymer, an ion and an ionic polymer electrolyte.

As one example, the continuous inert gas injection may be performed from the start of the reaction to the end of the reaction.

As another example, the continuous inert gas injection may be intermittently repeatedly injected with an inert gas or intermittently injected continuously.

Specifically, the term "continuous" in the present invention means the time of the overall process in which the reaction proceeds in the reaction vessel. Injecting the inert gas continuously does not limit the continuous injection during the process . For example, the reaction vessel may be filled with inert gas before the start of the reaction, and inert gas may be continuously injected from the beginning of the reaction to the end of the reaction. For example, as described above, it is possible to intermittently inject repeatedly at a predetermined time interval from the beginning of the reaction to the end of the reaction, or to continuously inject intermittently.

The conductive polymer, ion, and ionic polymer electrolyte may be present in the solvent. Distilled water may be used as the solvent. Specifically, the conductive polymer may be present in the form of particles in distilled water. By using distilled water as a solvent instead of an organic solvent, environmental pollution can be reduced.

The conductive polymer, ion, and ionic polymer electrolyte are described below, and the same applies to each component described in the description of the apparatus.

The conductive polymer may be at least one selected from the group consisting of, for example, poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid, polypyrrole: polystyrene sulfonic acid, and polythiophene: polystyrene sulfonic acid. Specifically, the conductive polymer may include, but is not limited to, poly (3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PP), and polythiophene (PT). The conductive polymer may be uncharged or cationic.

The poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT: PSS), polypyrrole: polystyrene sulfonic acid (PP: PSS) and polythiophene: polystyrene sulfonic acid (PT: PSS) May be 0.1 to 10 parts by weight, based on the weight parts. For example, the conductive polymer may include 0.1 to 8 parts by weight, 0.5 to 7 parts by weight, 1 to 5 parts by weight, or 3 to 8 parts by weight. The conductive polymer can be appropriately adjusted within the content range of the conductive polymer and manufactured into a composition suitable for a desired product and used in various applications.

For example, the conductive polymer may be a cation. Where "cation" may relate only to the charge present on the main chain. Therefore, the conductive polymer may require anion to compensate for the positive charge. The anion may be obtained from an ionic polymer electrolyte, and examples of the ionic polymer electrolyte may include a monomer anion or a polyanion having a molecular weight of 20,000 to 1,000,000.

Examples of such monomeric anions include, but are not limited to, C ₁ -C ₂₀ -alkanesulfonic acid, aliphatic perfluorosulfonic acid, aliphatic C ₁ -C ₂₀ -carboxylic acid, aliphatic perfluorocarboxylic acid, C ₁ -C ₂₀ -alkyl groups Such as aromatic sulfonic acid, cycloalkanesulfonic acid, iron sulfate, sodium persulfate, tetrafluoroborate, hexafluorophosphate, perchlorates, hexafluoroantimonate, hexafluoroarsenate, And may include hexafluoroarsenates or hexachloroantimonates.

Examples of such polyanions include anions of polymeric carboxylic acids (e.g., polyacrylic acid, polymethacrylic acid or polymaleic acid), polymeric sulfonic acids (e.g., polystyrene sulfonic acid and polyvinyl sulfonic acid) and poly Sulfonic-co-maleic acid). Specifically, the ionic polymer electrolyte may be polystyrene sulfonic acid having a molecular weight of 20,000 to 1,000,000.

As a result, ions such as positive ions and anions may be present in the solution during the formation of the coupling structure.

The conductive polymer solution containing the conductive polymer, ion, and ionic polymer electrolyte may further include a polymer binder. The polymeric binder may include, for example, polymeric organic binders such as polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl chloride, polyvinylacetate, polyvinyl butyrate, polyacrylic acid ester, polyacrylamide, Acrylic acid esters, ethylene / vinyl acetate copolymers, polybutadienes, polyisoprenes, polystyrenes, polyethers, polyesters, polycarbonates, polyacrylates, , Polyurethane, polyamide, polyimide, polysulfone, melamine-formaldehyde resin, epoxy resin, silicone resin and cellulose.

The conductive polymer, the ion, and the conductive polymer solution containing the ionic polymer electrolyte may further include an adhesion promoter. The adhesion promoter may, for example, comprise organofunctional silanes or hydrolyzates thereof. The hydrolyzate may be, for example, 3-glycidyloxypropyltrialkoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, -mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and octyltriethoxysilane.

Polystyrene sulfonic acid (PEDOT: PSS), polypyrrole: polystyrene sulfonic acid (PP: PSS) and polythiophene: polystyrenesulfonic acid (PT: PSS), which are the conductive polymers, May be included in a weight ratio of 1: 1 to 1:20. For example, the weight ratio can be included in a weight ratio of 1: 1.6, 1: 2.5, 1: 3, 1: 5, 1: 6, 1: 7.5 or 1:10.

The solution containing the conductive polymer, ion and ionic polymer electrolyte may further contain a dopant.

For example, the dopant may include at least one selected from the group consisting of ammonium salt electrolytes, sodium salt electrolytes, lithium salt electrolytes, iron salt electrolytes, sulfonic acid compounds, and sulfuric acid. For example, the dopant is not particularly limited, but may include organic compounds containing oxygen and nitrogen.

The ammonium salt electrolyte may include at least one of tetra-n-Bu ₄ NClO ₄ , n-Bu ₄ NPF ₆ , n-Bu ₄ NBF ₄ and n-Et ₄ NClO ₄ .

The sodium salt electrolyte may include, for example, at least one of NaPF ₆ , NaBF _4, and NaClO ₄ .

The lithium salt electrolyte, for _{example, LiClO 4, LiPF 6, LiBF} 4, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiCF 3 SO 3, LiC (SO 2 CF 3 _{) 3, LiPF 4 (CF 3} ) 2, LiPF 3 (C 2 F 5) 3, LiPF 3 (CF 3) 3, LiPF 3 (iso-C 3 F 7) 3, LiPF 5 (iso-C 3 F 7 ) And a lithium salt electrolyte having a cyclic alkylene group.

For example, the lithium salt having a cyclic alkylene group may include (CF ₂ ) ₂ (SO ₂ ) ₂ NLi and (CF ₂ ) ₃ (SO ₂ ) ₂ NLi.

The iron salt electrolyte may include, for example, iron (III) oxide p-toluenesulfonic acid.

The sulfonic acid compound is, for example, an alkanesulfonic acid having 1 to 20 carbon atoms, a perfluoroalkanesulfonic acid having 1 to 20 carbon atoms, an alkylhexylcarboxylic acid having 1 to 20 carbon atoms, a purple having 1 to 20 carbon atoms An aromatic sulfonic acid substituted or unsubstituted by an alkyl group having 1 to 20 carbon atoms, and a cycloalkanesulfonic acid (e.g., camphorsulfonic acid).

Specifically, the sulfonic acid compound may be selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, octadecanesulfonic acid, nonadecanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutane Sulfonic acid, perfluorooctanesulfonic acid, ethylhexylcarboxylic acid, benzenesulfonic acid, o -toluenesulfonic acid, p -toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, P-toluenesulfonic acid and p-toluenesulfonic acid.

The dopant may be discontinued or a mixture of two or more dopants may be used.

For example, the dopant may be either a sulfuric acid or a sulfonic acid compound, or two or more thereof.

The dopant may be dissolved and mixed in a solvent.

The solvent used in mixing the dopant is not particularly limited as long as it can dissolve the dopant and can be mixed with water. For example, the solvent may be at least one selected from the group consisting of water, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetonitrile, and an alcohol-based solvent.

Under said continuous inert gas injection conditions,

After the step of preparing a solution containing a conductive polymer, an ion and an ionic polymer electrolyte,

And then filtering the prepared solution using a filtration membrane.

The step of filtering the prepared solution using a filtration membrane comprises:

After mixing the conductive polymer solution and the dopant, the unreacted dopant can be removed by filtration. For example, in the course of mixing the conductive polymer solution and the dopant, the dopant may be doped in the conductive polymer. In this case, when the unreacted dopant that is not doped in the conductive polymer is excessive, The electric conductivity may be lowered. Therefore, the unreacted dopant can be removed by filtration to prevent a decrease in electric conductivity.

As the filtration method, for example, filtration under pressure in addition to micro filtration, ultrafiltration, reverse osmosis or hyper filtration and dialysis may be carried out according to a filtration method, And the like. Depending on the module used, filtration methods including spiral-wound, tubular, hollow-fiber, plate & frame, monolith type, etc. may be used .

A conductive polymer film having an electrical conductivity of 500 S / cm or more can be prepared using the conductive polymer solution prepared in the present invention.

The electrical conductivity of the conductive polymer film within the above range may mean a low sheet resistance. As a result, high performance can be achieved when applied to electronic devices.

Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the scope of the present invention is not limited by the following Examples.

Example  One

12.53 g of polystyrene sulfonic acid (PSS) was dissolved in 1400 g of distilled water and stirred using an impeller for 1 hour. Then, 0.2 g of iron sulfate was added and stirred until it was dissolved. When all of the iron sulfate was dissolved, the temperature of the solution was lowered to 13 ° C. Then 5.014 g of 3,4-ethylenedioxythiophene (EDOT) monomer was added, and 11.9 g of sodium persulfate Was added to 30 g of the aqueous solution. Then, nitrogen was added immediately at a flow rate of 100 L / min to lower the oxygen concentration in the solvent to 1000 ppb or less. After the polymerization reaction was carried out for 24 hours in this state, the cation exchange resin and the anion exchange resin were mixed at a ratio of 1: 1 was mixed with 500 ml of mixed ion exchange resin to remove unnecessary ions to prepare a conductive polymer solution. During the manufacturing process, oxygen was continuously removed by intermittently supplying nitrogen gas to prevent the conductive polymer solution material from contacting the generated oxygen. The nitrogen gas was injected at a flow rate of 100 L / min, and the pressure inside the reactor was maintained at 1.3 atm.

The prepared conductive polymer solution was prepared as a 1.3% concentration solution, and 5% DMSO solution was added to the solution. The resulting solution was thoroughly mixed, coated with a bar coating, and dried at 150 ° C for 30 minutes to prepare a conductive polymer film .

Example  2

In the same manner as in Example 1, the injected nitrogen gas was intermittently injected repeatedly at intervals of a predetermined time so that the conductive polymer solution material did not come into contact with the generated oxygen during the manufacturing process. Specifically, intermittent injection was repeated at a flow rate of 100 L / min for 2 hours and stopped for 30 minutes. Through this, the internal pressure of the reactor was maintained at 1.3 atm while nitrogen was being injected, and the inside of the reactor was filled with nitrogen even when not injected, so that air contact with the outside could be prevented.

Example  3

After the ion exchange resin was removed, 100 ml of a 0.05 wt% sulfuric acid aqueous solution as a dopant was added to the conductive polymer solution, followed by stirring.

Example  4

After the ion exchange resin was removed, 100 ml of a 0.05 wt% sulfuric acid aqueous solution as a dopant was added to the conductive polymer solution, followed by stirring. Then, the solution was further subjected to filtration by ultrafiltration using a membrane membrane having a pore size of 100 nm. At this time, distilled water was continuously introduced and filtered. Through this, components other than PEDOT: PSS polymer particles were removed. As a result, it was confirmed that the solution filtered through the filtration membrane was an acidic solution having a pH of 4 or less and a solution containing PSS as an acid substance.

Example  5

The conductive polymer film was prepared in the same manner as in Example 4, except that the dopant was mixed in an amount of 3000 ml.

Example  6

The conductive polymer film was prepared in the same manner as in Example 4 except that the dopant was introduced at a concentration of 3000 ml and the dopant was introduced and distilled water was filtered at the same time.

Example  7

Was prepared in the same manner as in Example 4, except that 3000 ml of p-toluenesulfonic acid as a dopant was mixed to prepare a conductive polymer film.

Example  8

Toluenesulfonic acid as a dopant, and conducting filtration using a dopant and distilled water at the same time, to prepare a conductive polymer film. The conductive polymer film was prepared in the same manner as in Example 4, except that 3000 ml of p-toluenesulfonic acid was used as a dopant.

Example  9

A conductive polymer film was prepared using the CLEVIOS PH1000 solution of Heraeus as a conductive polymer solution in the same manner as in Example 4 above.

Example  10

A conductive polymer film was prepared in the same manner as in Example 4 except that CLEVIOS PH1000 solution of Heraeus was used as a conductive polymer solution and dopant was mixed in 500 ml in different amounts.

Example  11

A conductive polymer film was prepared in the same manner as in Example 4 except that CLEVIOS PH1000 solution of Heraeus was used as the conductive polymer solution and the dopant was mixed in the amount of 3000 ml in different amounts.

Example  12

The same procedure as in Example 4 was carried out except that CLEVIOS PH1000 solution of Heraeus was used as a conductive polymer solution and the dopant was introduced at a concentration of 3000 ml and filtration with distilled water was carried out at the same time, To prepare a polymer film.

Example  13

A conductive polymer film was prepared in the same manner as in Example 4 except that CLEVIOS PH1000 solution of Heraeus was used as a conductive polymer solution and 3000 ml of p-toluenesulfonic acid was mixed as a dopant.

Example  14

CLEVIOS PH1000 solution of Heraeus was used as a conductive polymer solution, and 3000 ml of p-toluenesulfonic acid was doped as a dopant. Filtration using the dopant and distilled water were carried out in the same manner as in Example 4 To prepare a conductive polymer film.

Comparative Example  One

The conductive polymer film was prepared in the same manner as in Example 1, except that no nitrogen gas was added during the production process.

Comparative Example  2

A conductive polymer film was prepared in the same manner as in Example 1 except that the inside of the reaction vessel was evacuated using a vacuum pump without introducing nitrogen gas during the production process.

Comparative Example  3

The nitrogen gas was injected at a flow rate of 5 L / min during the manufacturing process. At this time, the pressure inside the reaction vessel was maintained at 1 atm.

Experimental Example

Electrical conductivity measurements were conducted on the conductive polymer films prepared in Examples 1 to 14 and Comparative Examples 1 and 2. The results are shown in Table 1 below.

Electrical Conductivity (S / cm) Example 1 615 Example 2 513 Example 3 781 Example 4 1532 Example 5 1597 Example 6 1733 Example 7 772 Example 8 1482 Example 9 1513 Example 10 1525 Example 11 1537 Example 12 1680 Example 13 1546 Example 14 1625 Comparative Example 1 150 Comparative Example 2 540

As shown in Table 1, when the conductive polymer films prepared in Examples 1 to 14 according to the present invention were compared with the conductive polymer films prepared in Comparative Example in which no nitrogen gas was continuously injected during the manufacturing process under the same conditions, And it was confirmed that it exhibited higher electric conductivity values.

In addition, the conductive polymer films prepared in Example 1 and Comparative Example 2 exhibited similar electrical conductivity, but compared with Comparative Example 2 using a vacuum pump, the conductive polymer films obtained in Example 1 using an inert gas exhibited somewhat higher electrical conductivity .

100, 200, 300, 400: reaction vessel
110, 210, 310, 410: inert gas injection unit
120, 220, 320, 420: gas outlet
130, 230, 330, 430: Cooling circulation device

Claims (17)

A reaction container comprising a solution containing a conductive polymer, an ion and an ionic polymer electrolyte;
And an inert gas injection unit for continuously injecting the inert gas into the solution contained in the reaction vessel for a period of time during which the reaction proceeds,
Wherein the reaction vessel has an average pressure over 1 atm during the course of the reaction. The method according to claim 1,
Wherein the solution containing the conductive polymer, ion and ionic polymer electrolyte contained in the reaction vessel further contains a dopant. The method according to claim 1,
Characterized in that the reaction vessel is filled with an inert gas prior to the initiation of the reaction. The method according to claim 1,
Further comprising a filtration section for performing filtration by supplying a reaction-completed solution in the reaction vessel. The method according to claim 1,
Wherein the reaction vessel further comprises a gas outlet. 6. The method of claim 5,
Wherein the gas outlet is formed in an upper region of the reaction vessel which is not immersed by the solution. The method according to claim 1,
Wherein the reaction vessel further comprises a cooling circulation device. The method according to claim 1,
Wherein the inert gas injection portion is divided into a plurality of injection portions on the same plane in the reaction vessel. The method according to claim 1,
Wherein the inert gas injection portion is formed by dividing the inert gas injection portion into the same plurality of injection portions in a plane having different heights in the reaction vessel. The method according to claim 1,
Wherein the inert gas injection portion is formed at a position where the inert gas injection portion is immersed by the solution in the reaction vessel. Continuously injecting an inert gas, and under pressure conditions exceeding 1 atm,
A method for producing a conductive polymer solution, comprising the steps of: preparing a solution containing a conductive polymer, an ion, and an ionic polymer electrolyte. 12. The method of claim 11,
Wherein the continuous inert gas injection is performed from the start of the reaction to the end of the reaction. 12. The method of claim 11,
Wherein the continuous inert gas injection is performed by intermittently injecting an inert gas repeatedly or continuously intermittently injecting an inert gas. 12. The method of claim 11,
Wherein the conductive polymer is at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid, polypyrrole: polystyrene sulfonic acid, polythiophene: polystyrene sulfonic acid and polyaniline: polystyrene sulfonic acid A method for producing a conductive polymer solution. 12. The method of claim 11,
Wherein the solution containing the conductive polymer, the ion and the ionic polymer electrolyte further contains a dopant. 16. The method of claim 15,
Wherein the dopant is at least one selected from the group consisting of ammonium salt electrolytes, sodium salt electrolytes, lithium salt electrolytes, iron salt electrolytes, sulfonic acid compounds, and sulfuric acid. 12. The method of claim 11,
After the step of preparing a solution containing a conductive polymer, an ion and an ionic polymer electrolyte,
The method of claim 1, further comprising the step of filtering the prepared solution using a filtration membrane.

Images