KR101619130B1 - Manufacturing method of conductive polymer solution and device manufacturing for the same - Google Patents

Abstract

The present invention relates to a method of manufacturing a conductive polymer solution and an apparatus for manufacturing the conductive polymer solution, wherein the conductive polymer solution can be produced by injecting a metal catalyst and hydrogen gas, thereby removing oxygen generated in the manufacturing process, The oxidation of the polymer can be prevented, the electrical conductivity can be increased, and the manufacturing cost can be reduced.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a conductive polymer solution and a device for manufacturing the conductive polymer solution,

The present invention relates to a method for producing a conductive polymer solution and an apparatus for manufacturing 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.

In order to form the transparent electrode, it is preferable to use a conductive polymer having high conductivity. As a method of synthesizing the conductive polymer having the high conductivity, a vacuum process method in which a polymerization reaction is performed after lowering the inside of a reaction vessel to a pressure lower than atmospheric pressure using a vacuum pump, or a polymerization method using an inert gas has been performed. Generally, when PEDOT: PSS is synthesized, an ionic oxidizing agent containing Fe ^{+ 3} and an ionic oxidizing agent containing persulfate are used together to cause the oxidation reaction to cause the polymerization of the EDOT monomer. At this time, sodium persulfate (SPS) and potassium persulfate (KPS), which are potassium-based oxidizing agents, are frequently used. These oxidants are dissolved in water and react with water to generate oxygen as a by- . When reduced by Fe ⁺² , S ₂ O ₆ ^{2 -} ions react with water to generate oxygen. At this time, oxygen generated may oxidize the EDOT monomer to decrease the conductivity, and it may interfere with the polymerization to generate PEDOT having a low molecular weight, resulting in lowering the conductivity of the conductive polymer as the final product. When oxygen generated through this chemical reaction is polymerized under vacuum, oxygen can be removed by a pump and polymerization reaction can be performed. This is to prevent oxidation of PEDOT due to oxygen generated in this process. 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 polymerization is carried out under vacuum, evaporation of the liquid monomer and the solvent may occur, resulting in the loss of the monomer of the solvent, and not only the same property can not be obtained every time the reaction is performed under the same conditions, . Further, since the evaporation of water is not constant, it is difficult to control the concentration and viscosity of the polymerization process using a vacuum, and when the vacuum is broken, desired physical properties can not be obtained. In another method, when the conductive polymer is polymerized by using an inert gas such as nitrogen, the conductivity can be improved by a method of initiating the reaction after removing oxygen dissolved in the solvent with nitrogen gas. However, compared with the method using a vacuum It has low conductivity and low conductivity for use as a transparent electrode. When nitrogen gas is used, a large amount of bubbles are generated by PSS, which is a polymer electrolyte, for a certain period of time or continuously in the solution, so that the reaction solution may overflow and the homogeneous reaction may not occur, thereby deteriorating the physical properties of the final solution Have.

Korean Patent Publication No. 2012-0077112

The present invention relates to a method for producing a conductive polymer solution and an apparatus for manufacturing the same, wherein the conductive polymer solution can be prepared under the conditions of a metal catalyst and hydrogen gas.

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

Under the conditions of supplying the metal catalyst and the hydrogen gas,

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

In addition, 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;

A catalyst supporting part which is contained in the reaction vessel and supports a metal catalyst; And

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

By manufacturing the conductive polymer solution through the manufacturing method and apparatus according to the present invention, it is possible to prevent the oxidation of the conductive polymer by removing oxygen generated in the manufacturing process, to increase the electric conductivity, and to lower the production cost.

1 and 2 are each a schematic diagram of an apparatus according to the invention, in one embodiment.

The present invention relates to a method for producing a conductive polymer solution and an apparatus for manufacturing the same.

As one example of the method for producing the conductive polymer solution,

Under the conditions of supplying the metal catalyst and the hydrogen gas,

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

Specifically, a metal catalyst is present and oxygen generated during the manufacturing process and oxygen present in the solution can be removed by preparing the conductive polymer under the condition of continuously injecting hydrogen gas. Thus, the produced conductive polymer can realize a high electric conductivity.

The catalyst may include a particulate metal catalyst or a resin carrying a metal catalyst.

The metal catalyst or the metal catalyst supported on the metal catalyst is not particularly limited as long as the metal catalyst is a metal having hydrogenation characteristics. For example, the metal catalyst may be at least one of the transition metals.

The metal catalyst may include at least one of palladium, platinum, rhodium, nickel and iron. For example, the metal catalyst may be palladium, palladium-platinum, palladium-rhodium, palladium-nickel, or palladium- It can be iron.

The resin surrounding the metal catalyst may be appropriately selected so as not to affect the production process in the production of the conductive polymer. For example, a cation exchange resin can be used. The cation exchange resin may be a conventionally used cation exchange resin, for example, a sulfone-based or carboxyl-based cation exchange resin may be used.

By using the resin on which the metal catalyst is supported, the solution stability of the metal catalyst can be imparted, and the catalyst can be recovered easily later.

The conditions for supplying the metal catalyst and the hydrogen gas are,

The metal catalyst is continuously present from the start of the reaction until the end of the reaction,

Wherein the hydrogen gas is injected repeatedly intermittently before the start of the reaction until the end of the reaction or continuously injected continuously intermittently.

For example, the metal catalyst may be supported in a network having a mesh structure of micro unit before the initiation of the reaction. By using the above net, the catalyst can be prevented from being broken by stirring, and the catalyst can be fixed easily, and the catalyst can be easily recovered after completion of the reaction.

Specifically, the term "continuous" in the present invention means an overall process time in which the reaction proceeds in the reaction vessel, and continuously injecting hydrogen gas does not limit the continuous injection of the process . For example, the reaction vessel may be filled with hydrogen gas before the start of the reaction, and hydrogen 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. Here, the conductive polymer, ion, and ionic polymer electrolyte are described as follows, and the same can be applied to each component described in the description of the apparatus.

The hydrogen gas may be a gas containing hydrogen or a mixed gas of hydrogen and an inert gas. For example, when there is a defect in the apparatus, there is a risk of explosion when hydrogen gas of high purity is used, and hydrogen and an inert gas can be mixed and used.

For example, the step of preparing a solution containing the conductive polymer, ion, and ionic polymer electrolyte includes:

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

Preparing a solution containing a mixture of an ionic polymer electrolyte and deoxygenated distilled water; And

And mixing the solution with a conductive polymer monomer, an ion and an initiator.

Specifically, the conductive polymer monomer, the ion and the initiator may be mixed after first mixing and stirring the ionic polymer electrolyte and the deoxygenated distilled water of 5 ppb or less in which oxygen is removed by using a membrane degasser.

By using deoxygenated distilled water in which oxygen is removed by using the membrane degassing, a large amount of oxygen is removed in advance before the reaction to prevent the peroxidation reaction of the conductive polymer, whereby a conductive polymer having high conductivity can be produced .

Here, the initiator is not particularly limited as long as it is a chemical species capable of causing polymerization.

The conductive polymer may be an optionally substituted polypyrrole, polyaniline or polythiophene.

For example, the conductive polymer may include a structure represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

X and Y each independently represent O, S, Si or N,

R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,

n is an integer from 2 to 2000,

Alternatively, R ₁ and R ₂ are bonded to each other to represent a fused ring structure.

At this time, the alkyl group may mean a functional group derived from a linear or branched saturated hydrocarbon.

Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1,1-dimethylpropyl group, , 2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, Methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2- Dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group and 3-methylpentyl group.

In addition, the aryl group may mean a monovalent substituent derived from an aromatic hydrocarbon.

Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a naphthacenyl group, a pyrenyl group, A tolyl group, a biphenylyl group, a terphenyl group, a chrycenyl group, a spirobifluorenyl group, a fluoranthenyl group, a fluorene group, A perfluoroalkyl group, a fluorenyl group, a perylenyl group, an indenyl group, an azulenyl group, a heptalenyl group, a phenalenyl group, a phenanthrenyl group, group).

Further, the heteroaryl group represents an aromatic heterocycle or a heterocyclic group derived from a monocyclic or condensed ring. The heteroaryl group may include at least one of nitrogen (N), sulfur (S), oxygen (O), phosphorus (P), selenium (Se), and silicon (Si) as a heteroatom.

Specific examples of the heteroaryl group include pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazolyl, tetrazolyl, benzotriazolyl, pyrazolyl, imidazolyl, An imidazolyl group, an imidazolyl group, a thiazolyl group, an isothiazolyl group, a benzothiazolyl group, a benzothiadiazolyl group, a phenothiazyl group, an isoxazolyl group, a furazanyl group, a phenoxazinyl group, , A benzooxazolyl group, an oxadiazolyl group, a pyrazoloxazolyl group, an imidazothiazolyl group, a thienopuranyl group, a furopyrrolyl group, and a pyridoxazinyl group.

As an example, the conductive polymer may be represented by the following formula (1): K (K is an arbitrary integer between 2 and 2000) repeating structure, X, Y, R ₁ and R ₂ may be different from each other. For example, the conductive polymer represented by the structure of the formula (1) may be selected from the structures of the following formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

and n is an integer of 2 to 2000.

Specifically, the conductive polymer may be at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene): polystyrene sulfonic acid, polypyrrole: polystyrene sulfonic acid, and polythiophene: polystyrene sulfonic acid.

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 uncharged or cationic. 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. Thus, ions such as positive ions and anions may be present in the solution during the formation of the binding 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 of an ammonium salt electrolyte, a sodium salt electrolyte, a lithium salt electrolyte, an iron salt electrolyte, a sulfonic acid compound, 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 include at least one of water, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetonitrile, and an alcohol-based solvent.

After the step of preparing a solution containing the conductive polymer, ion and 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 electric conductivity of 800 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.

In addition, the present invention can provide an apparatus for producing a conductive polymer.

As an example of such an apparatus,

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

A catalyst supporting part which is contained in the reaction vessel and supports a metal catalyst; And

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

Specifically, a reaction vessel containing a solution containing a conductive polymer, an ion, and an ionic polymer electrolyte, and a catalyst supporting unit in the reaction vessel, and a hydrogen gas injecting unit connected to the reaction vessel through which intermittent or intermittent It is possible to perform continuous injection of hydrogen gas.

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 problem can be prevented by removing oxygen generated during the reaction in the reaction vessel using the catalyst and the hydrogen gas injected through the catalyst injecting unit and the hydrogen gas injecting unit. For example, the higher the purity of the catalyst and the hydrogen gas injected through the hydrogen gas injecting unit, the easier it is to remove oxygen, and the conductive polymer having a high electrical conductivity can be produced.

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 conventionally removed through a vacuum process using a vacuum pump or hydrogen gas injection, but there are many problems as described above. In the present invention, the oxygen generated may be injected into the catalyst and hydrogen gas to convert oxygen generated during the production process or oxygen present in the solution into water, thereby removing the oxygen in the reactor.

Specifically, the catalyst existing in the conductive polymer solution has the hydrogenation reaction characteristic, and is combined with the hydrogen of the injected hydrogen gas. At this time, hydrogen bonded to the catalyst is converted into water by reacting with oxygen in the reactor, thereby solving the problems that may occur due to oxygen in the process of manufacturing the conductive polymer.

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

Here, the conductive polymer, the ion, the ionic polymer electrolyte, the catalyst, and the dopant may be the same as those described above.

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. The filtration membrane is not particularly limited as long as it 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, it is possible to prevent excessive pressure from being applied to the apparatus due to the hydrogen gas continuously flowing through the hydrogen gas inlet.

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. As a result, it is possible to solve problems such as device corrosion due to water vapor generated in the reaction vessel.

The apparatus according to the present invention can be explained with reference to Figs. 1 and 2. Fig. Referring to Figures 1 and 2, the reaction vessel 100, 200 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 equipped with an impeller, and a metal catalyst 120, And hydrogen gas injecting parts 130 and 230 connected to the solution from a bomb (not shown), and gas outlets 140 and 240 located above the reaction vessel And a cooling circulation device (150, 250) connected to the reaction vessel.

At this time, in Fig. 1 and Fig. 2, the positions of the catalyst supporting portions may be different from each other.

As one example, the catalyst supporting portion can be removed by being installed on the inner wall of the reaction vessel and coming into contact with oxygen in the reaction vessel and converting the oxygen to water. This can be confirmed from FIG. Specifically, it is confirmed that the catalyst supporting portion 110 shown in FIG. 1 is installed on the inner wall surface of the reaction vessel 100 to remove oxygen from the reaction vessel.

As another example, the catalyst supporting portion may be provided on the rotating shaft of the impeller installed in the reaction vessel. This can be confirmed from FIG. Specifically, the catalyst supporting portion 210 shown in Fig. 2 is provided on the rotating shaft of the impeller installed in the reaction vessel 200, and is brought into contact with oxygen existing in the reaction vessel in accordance with the rotation of the impeller, Can

Further, in the apparatus according to the present invention, the position of the hydrogen gas injection portion can be selectively changed.

As another example, the hydrogen gas injecting section may be formed by dividing the hydrogen gas injecting section into a plurality of injection sections on the same plane in the reaction vessel, as shown in Figs. Thus, hydrogen gas can be uniformly supplied into the reaction vessel.

As another example, the hydrogen gas injecting section may be formed by dividing the same into a plurality of injection sections in a plane having different heights in the reaction vessel. Specifically, the hydrogen gas injecting section is formed on the side surface of the reaction vessel, and is provided with a plurality of injection sections on a plane having different heights, so that hydrogen gas can be uniformly supplied to the solution in the reaction vessel.

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 in a reaction vessel having a catalyst supported thereon, followed by stirring with an impeller for 2 hours under the injection of hydrogen gas. 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. After polymerization reaction for 24 hours, 500 ml of a mixed ion exchange resin in which 1: 1 cation exchange resin and anion exchange resin were mixed was removed to remove unnecessary ions to prepare a conductive polymer solution.

On the other hand, in order to remove oxygen generated during the manufacturing process, hydrogen gas was continuously injected into the lower part of the reactor. The hydrogen gas was injected at a flow rate of 30 L / min.

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

Hydrogen gas was injected intermittently 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, a flow rate of 20 L / min was injected at a time interval of 1 hour.

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.

Example  15

The conductive polymer film was prepared in the same manner as in Example 1 except that distilled water having an oxygen concentration of 5 ppb purified by membrane degassing was used as distilled water.

Comparative Example  One

A conductive polymer film was prepared by injecting nitrogen gas as an inert gas instead of injecting catalyst and hydrogen gas during the manufacturing process.

Comparative Example  2

The conductive polymer film was prepared in the same manner as in Example 1 except that the inside of the reaction vessel was evacuated by using a vacuum pump instead of injecting the catalyst and hydrogen gas during the manufacturing process.

Experimental Example

The conductivity measurement of the conductive polymer films prepared in Examples 1 to 15 and Comparative Examples 1 and 2 was conducted. The results are shown in Table 1 below.

Electrical Conductivity (S / cm) Example 1 821 Example 2 830 Example 3 987 Example 4 1680 Example 5 1890 Example 6 1695 Example 7 1705 Example 8 1725 Example 9 1510 Example 10 1615 Example 11 1672 Example 12 1693 Example 13 1627 Example 14 1688 Example 15 988 Comparative Example 1 335 Comparative Example 2 715

As shown in Table 1, the conductive polymer films prepared in Examples 1 to 15 according to the present invention were prepared by using the conductive polymer film of Comparative Example 1 prepared by introducing nitrogen gas, which is an inert gas, It was confirmed that they exhibited the same or higher electric conductivity values as compared with Comparative Example 2 prepared in Comparative Example 1. [

100, 200: reaction vessel
110, 210: catalyst supporting portion
120, 220: metal catalyst
130, 230: hydrogen gas injection unit
140, 240: gas outlet
150, 250: cooling circulation device

Claims (18)

Under a supply condition of hydrogen gas supplied to a hydrogen gas injection unit connected to a reaction vessel containing a metal catalyst and a conductive polymer solution supported and supported in a mesh having a mesh unit of micro unit,
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.
The method according to claim 1,
Wherein the metal catalyst comprises a particulate metal catalyst or a resin carrying a metal catalyst.
The method according to claim 1,
Wherein the metal catalyst comprises at least one transition metal.
The method of claim 3,
Wherein the metal catalyst is at least one of palladium, platinum, rhodium, nickel and iron.
The method according to claim 1,
The conditions for supplying the metal catalyst and the hydrogen gas are as follows:
The metal catalyst is continuously present from the start of the reaction until the end of the reaction,
Wherein the hydrogen gas is injected repeatedly intermittently before the start of the reaction until the end of the reaction or continuously injected continuously intermittently.
The method according to claim 1,
Wherein the hydrogen gas is a gas containing hydrogen or a mixed gas of hydrogen and an inert gas.
The method according to claim 1,
The step of preparing a solution containing a conductive polymer, an ion and an ionic polymer electrolyte,
Preparing a solution containing a mixture of an ionic polymer electrolyte and deoxygenated distilled water; And
And mixing the solution with a conductive polymer monomer, an ion and an initiator.
The method according to claim 1,
Wherein the conductive polymer comprises a structure represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In Formula 1,
X and Y each independently represent O, S, Si or N,
R ₁ and R ₂ each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, or a heteroaryl group having 2 to 20 carbon atoms,
n is an integer from 2 to 2000,
Alternatively, R ₁ and R ₂ are bonded to each other to represent a fused ring structure.
9. The method of claim 8,
The K repeating structure of K (K is an arbitrary integer of 2 to 2000) of the formula (1) has, in the definition of formula (1), X, Y, R ₁ and R ₂ Wherein at least one of them is different.
10. The method of claim 9,
Wherein the conductive polymer represented by the formula (1) is selected from the following formulas (2) to (4):
(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,
and n is an integer of 2 to 2000.
The method according to claim 1,
Wherein the solution containing the conductive polymer, the ion and the ionic polymer electrolyte further contains a dopant.
12. The method of claim 11,
Wherein the dopant is at least one of an ammonium salt electrolyte, a sodium salt electrolyte, a lithium salt electrolyte, an iron salt electrolyte, a sulfonic acid compound, and sulfuric acid.
The method according to claim 1,
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.
A reaction container comprising a solution containing a conductive polymer, an ion and an ionic polymer electrolyte;
A catalyst supporting part which is contained in the reaction vessel and supports a metal catalyst; And
And a gas injection unit for continuously injecting hydrogen gas into the solution contained in the reaction vessel for a period of time during which the reaction proceeds.
15. The method of claim 14,
Wherein the solution containing the conductive polymer, ion and ionic polymer electrolyte contained in the reaction vessel further contains a dopant.
15. The method of claim 14,
Further comprising a filtration section for performing filtration by supplying a reaction-completed solution in the reaction vessel.
15. The method of claim 14,
And the catalyst supporting portion is formed on the inner wall of the reaction vessel.
15. The method of claim 14,
Further comprising an impeller in the reaction vessel,
And the catalyst supporting portion is formed on the rotating shaft of the impeller.

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