KR101623195B1 - Preparation method of conductive polymer nano-marterial - Google Patents
Preparation method of conductive polymer nano-marterial Download PDFInfo
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- KR101623195B1 KR101623195B1 KR1020140163516A KR20140163516A KR101623195B1 KR 101623195 B1 KR101623195 B1 KR 101623195B1 KR 1020140163516 A KR1020140163516 A KR 1020140163516A KR 20140163516 A KR20140163516 A KR 20140163516A KR 101623195 B1 KR101623195 B1 KR 101623195B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
Abstract
Description
The present invention relates to a method for producing a conductive polymer nanomaterial, and more particularly, to a manufacturing method for easily mass-producing a polymer nanomaterial having excellent dispersibility, high heat resistance and electrical conductivity.
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.
Korean Patent No. 1420792 discloses a method of bonding an acidic dopant to a polyaniline polymer and then dedoping the acidic dopant using a basic compound and re-doping the acidic dopant into a sulfonic acid-based compound. However, this method also has a certain limit in mass production due to the characteristics of solution polymerization or emulsion polymerization, and the problem that the production cost of the final product increases due to the complexity of the production process and the cost structure is not completely solved.
Accordingly, there is a need to develop a method for mass production of polymer nanomaterials having excellent mechanical properties, high heat resistance and electrical conductivity.
The present invention is to provide a production method capable of easily mass-producing a polymer nanomaterial having excellent dispersibility, high heat resistance and electrical conductivity.
The present invention also provides a conductive polymer nanomaterial having excellent dispersibility, high heat resistance and electrical conductivity.
In the present specification, the step of mixing a polyaniline-based polymer by polymerizing a monomer microstructure, the first acidic dopant and an oxidizing agent of a polyaniline-based polymer; A dedoping step of reacting the polyaniline-based polymer microstructure with a basic compound; And kneading the doped polyaniline-based polymer microstructure and the second acidic dopant at a temperature of 40 to 230 ° C. The present invention also provides a method for producing a conductive polymer nanomaterial.
In the present specification, an aniline, an alkyl aniline having 1 to 5 carbon atoms, an alkoxy aniline having 1 to 5 carbon atoms, a dialkoxyaniline having 1 to 5 carbon atoms, a sulfonyl aniline, nitroaniline, pyrrole, ethylene dioxythiophene (EDOT) And a polymeric base material polymerized or copolymerized with at least one aniline monomer selected from the group consisting of an aniline monomer and an acid anhydride monomer, wherein at least 0.6 mol of an acidic dopant, relative to 1 mol of the aniline monomer, is bonded to the surface of the polymer base material, / RTI >
Hereinafter, a method for preparing a conductive polymer nanomaterial according to a specific embodiment of the present invention and a conductive polymer nanomaterial will be described in detail.
According to an embodiment of the present invention, there is provided a method for preparing a polyaniline-based polymer microstructure, which comprises polymerizing a polyaniline-based polymer microstructure by mixing a monomer of a polyaniline-based polymer, a first acidic dopant and an oxidizing agent; A dedoping step of reacting the polyaniline-based polymer microstructure with a basic compound; And kneading the doped polyaniline-based polymer microstructure and the second acidic dopant at a temperature of 40 to 230 ° C. The present invention also provides a method for producing a conductive polymer nanomaterial.
The present inventors have found that a polyaniline-based polymer microstructure is polymerized and an acidic dopant bonded to the polyaniline-based polymer microstructure is doped using a basic compound, and then the doped polyaniline-based polymer microstructure and the second acidic dopant are kneaded The polymer nanomaterial having excellent dispersibility, high heat resistance and electrical conductivity can be mass-produced more easily in a shorter time, and the invention is completed.
Particularly, by including the step of kneading the doped polyaniline-based polymer microstructure and the second acidic dopant, the total time for the entire manufacturing process can be greatly reduced, and the conductivity and dispersibility of the finally produced polymer nanomaterial can be improved, Heat resistance can be improved.
The step of kneading the doped polyaniline-based polymer microstructure with the second acidic dopant can further simplify the process steps and can be easily modified and applied to various process and application fields. In addition, Can be easily enlarged.
In the step of kneading the doped polyaniline-based polymer microstructure and the second acidic dopant at a temperature of 40 ° C to 230 ° C, or 80 ° C to 200 ° C, the doped polyaniline-based polymer microstructure and the second acidic dopant The second acidic dopant may be more uniformly brought into contact with the doped polyaniline-based polymer microstructure by more uniform contact with the doped polyaniline-based polymer microstructure, It is possible to combine more than the theoretical molar ratio with the acidic dopant, thereby being a polymer nanomaterial having excellent dispersibility and high conductivity and heat resistance.
The doped polyaniline-based polymer microstructure and the second acidic dopant may be kneaded at a temperature of 40 to 230 ° C. If the kneading temperature is too low, the second acidic dopant may be difficult to be bonded to the doped polyaniline-based polymer microstructure. If the temperature during kneading is too high, kneading of the doped polyaniline-based polymer microstructure and the second acidic dopant may be significantly deteriorated, and the second acidic dopant may be modified due to the high temperature, resulting in degradation of dispersibility and conductivity.
In the step of kneading the undoped polyaniline-based polymer microstructure and the second acidic dopant at a temperature of 40 to 230 ° C, the doped polyaniline-based polymer microstructure and the second acidic dopant are mechanically And the resulting mixture is kneaded. In the solvent state, when the doped polyaniline-based polymer microstructure and the second acidic dopant are bonded, it is difficult to bond at a theoretical molar ratio or more, so that a high dispersibility and a surface state can not be obtained when kneaded in a polymer resin.
In the step of kneading the doped polyaniline-based polymer microstructure and the second acidic dopant at a temperature of 40 to 230 ° C, a mechanical device such as a kneader, an extruder, a mixer, a screw mixer, a planetary mixer, The doped polyaniline-based polymer microstructure and the second acidic dopant may be mixed using a processing apparatus.
Specifically, the doped polyaniline-based polymer microstructure and the second acidic dopant may be allowed to remain in the mechanical processing apparatus for 10 to 1200 seconds to be kneaded. The kneading speed in the mechanical working apparatus or the rotating speed of the rotating portion in the apparatus is not limited to a great extent. The residence time is related to the binding of the material used in the kneading step. If the retention time is too long, structural defects of the doped polyaniline-based polymer microstructure and the second acidic dopant may be induced, or the second acidic dopant may be deformed due to heat generation due to shear stress with the screw. If the retention time is too small, the coupling between the doped polyaniline-based polymer microstructure and the second acidic dopant may not be sufficiently performed.
Meanwhile, the step of polymerizing the polyaniline-based polymer microstructure by mixing the monomers of the polyaniline-based polymer, the first acidic dopant, and the oxidizing agent may include a step of dispersing the monomers, the first acidic dopant, and the oxidant of the polyaniline- .
By dispersing the monomer of the polyaniline-based polymer and the first acidic dopant in an aqueous solution, the hydrogen ion of the acidic dopant can bond to the aniline-based monomer to form a micelle of anilinium cation . The polyaniline-based polymer microstructure may be formed by adding the oxidizing agent after dispersing the aniline monomer and the first acidic dopant in an aqueous solution. At this time, the oxidizing agent may serve as a polymerization initiator.
The polymerization may be carried out in a temperature range of -20 캜 to 80 캜, preferably -10 캜 to 60 캜, more preferably 0 캜 to 30 캜.
The polyaniline-based polymer microstructure may have a diameter of 1 nm to 500 nm.
As described above, the acidic dopant bonded to the surface of the polyaniline-based polymer microstructure can be dissociated through a dedoping step of reacting the polyaniline-based polymer microstructure with the basic compound. Such a step of dedoping can be performed at 0 캜 to 90 캜.
The compound that can be used as the basic compound is not particularly limited and can be used without any limitations as long as it can dedoped the acid dopant. For example, ammonium hydroxide, sodium hydroxide, lithium hydroxide, barium hydroxide, potassium hydroxide , Calcium hydroxide, or a mixture thereof.
The mole ratio of the polyaniline-based polymer microstructure: basic compound may be 1: 0.1 to 1:10, preferably 1: 0.9 to 1: 5 in the de-doping step.
The result obtained in the above-described de-doping step may be washed with an organic solvent such as alcohol or acetone to increase the purity.
Wherein the aniline monomer is selected from the group consisting of aniline, alkyl aniline having 1 to 5 carbon atoms, alkoxy aniline having 1 to 5 carbon atoms, dialkoxyaniline having 1 to 5 carbon atoms, sulfonyl aniline, nitroaniline, pyrrole, ethylenedioxythiophene (EDOT) And thiophenes. The term " a "
It said first acid dopant and the second acidic dopant are each sulfonic acid (sulfonic acid), selenite (selenic acid), phosphoric acid, boric acid, hydrogen sulphate (hydrogen sulfate), phosphate Flame (H 3 PO 4), benzene-sulfonic acid (BSA), benzene diisulfonic acid (BDSA), benzethytrisulfonic acid, benzene tetrasulfonic acid (BTSA), benzene peptasulfonic acid (BPSA), hydroxybenzenesulfonic acid (HBSA), hydroxydisulfonic acid, hydroxy (ABSA), camphorsulfonic acid (DBSA), dodecylbenzene disulfonic acid, dodecyl benzene disulfonic acid, alkyl benzene sulfonic acid (ABSA), camphorsulfonic acid (CSA), p-toluenesulfonic acid (TSA), naphthalenesulfonic acid (NSA), and naphthalene disulfonic acid (NDSA).
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 step of polymerizing the polyaniline-based polymer microstructure by mixing the monomers of the polyaniline-based polymer, the first acidic dopant, and the oxidizing agent may include the step of polymerizing monomers, primary acid dopants, oxidizing agents, and benzene rings of the polyaniline- Lt; RTI ID = 0.0 > a < / RTI > functional group.
A compound comprising a functional group in which at least one amine functional group is substituted on the benzene ring can initiate the 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 monomers of the first acidic dopant: polyaniline-based polymer may be 0.1: 1 to 10: 1.
The molar ratio of the oxidizing agent to the aniline monomer may be 0.1: 1 to 10: 1.
The molar ratio of the compound having a functional group in which at least one amine functional group is substituted in the monomer of the polyaniline-based polymer: benzene ring may be 1: 0.001 to 1:10.
The molar ratio of the doped polyaniline-based polymer microstructure: the second acidic dopant may be 1: 0.1 to 1: 2. If the molar ratio of the second acidic dopant is too small as compared with the doped polyaniline polymer microstructure, the doping effect may be deteriorated and the conductivity characteristics may be reduced. If the molar ratio of the second acidic dopant to the doped polyaniline-based polymer microstructure is too large, the site where the second acidic dopant can bind to the doped polyaniline-based polymer microstructure significantly exceeds the site, The slip effect can be greatly increased, resulting in a significant reduction in processability or migration.
Meanwhile, in the method for producing the conductive polymer nanomaterial, the first acidic dopant binds to the surface of the polyaniline-based polymer microstructure obtained in the polymerization process, and the first acidic dopant is doped using the basic compound. The second acidic dopant can be bonded to the position where the first acidic dopant is bonded.
When the second acidic dopant is reacted in solution rather than in the kneading process as in the previously known method, the amount of the second acidic dopant bound to the surface of the doped polyaniline-based polymer microstructure has a certain limit.
For example, when the doped polyaniline-based polymer microstructure and the second acidic dopant are reacted in a solution, the second acidic dopant is used as the repeating unit of the doped polyaniline-based polymer microstructure or the molar ratio of the second acidic dopant But only about 0.5 moles was bound. The bonding amount of the second acidic dopant can be derived by comparing and calculating the amount of the second acidic dopant remaining after the manufacturing step with respect to the usage amount.
On the other hand, according to the method for producing a conductive polymer nanomaterial of the embodiment, the second acidic dopant is used in an amount of 0.6 mol or more, or 0.6 mol to 1.5 mol, Mol, or from 0.7 mol to 1.3 mol.
Meanwhile, the step of kneading the doped polyaniline-based polymer microstructure and the second acidic dopant at a temperature of 40 to 230 ° C may include mixing the doped polyaniline-based polymer microstructure, the second acidic dopant, The method comprising the steps of: The additive means a general slip agent, a nucleating agent, a compatibilizer, a scavenger, an inorganic filler and the like, and examples thereof include an ethylene-maleic anhydride copolymer, a glycidyl-methacrylate copolymer, an ethylene- Acrylate copolymer, zinc stearate and zinc oxide, talc, whisker, calcium carbonate, sodium chloride, and the like.
According to another embodiment of the present invention, there is provided a process for producing an aniline compound, which comprises reacting aniline, alkyl aniline having 1 to 5 carbon atoms, alkoxy aniline having 1 to 5 carbon atoms, dialkoxy aniline having 1 to 5 carbon atoms, sulfonyl aniline, nitroaniline, pyrrole, (EDOT) and thiophene, wherein at least 0.6 mol of an acidic dopant, relative to 1 mol of the aniline monomer, is bonded to the surface of the polymer substrate , A conductive polymer nanomaterial may be provided.
The conductive polymer nanomaterial may be provided from the method for producing the conductive polymer nanomaterial of the embodiment described above.
The amount of the acidic dopant bonded to the surface of the conductive polymer nanomaterial has a certain limit when the acidic dopant is reacted in the solution as in the previously known method. For example, when the conductive polymer nanomaterial and the acidic dopant are reacted in solution, the acidic dopant alone is not bonded to the repeating unit of the conductive polymer nanomaterial or the one mole of the monomer used, to about 0.5 moles.
In contrast, in the method of manufacturing a conductive polymer nanomaterial according to one embodiment, the first acidic dopant binds to the surface of the polyaniline-based polymer microstructure obtained in the polymerization process, and the first acidic dopant is doped using a basic compound , And the second acidic dopant may be bonded to a position where the first acidic dopant is bonded through the kneading process.
An acidic dopant in an amount of 0.6 mol or more, or 0.6 mol to 1.5 mol, or 0.7 mol to 1.3 mol, based on 1 mol of the aniline monomer forming the polymer substrate in the finally produced conductive polymer nanomaterial, Lt; / RTI >
The conductive polymer nanomaterial has a diameter of 1 nm to 500 nm and an electrical conductivity at room temperature of 10 S / cm or more.
According to the present invention, there is provided a method of easily mass-producing a polymer nanomaterial having excellent mechanical properties, high heat resistance and electrical conductivity within a shorter time, and a conductive polymer nanomaterial having excellent mechanical properties, high heat resistance and electrical conductivity .
The conductive polymer material provided by the above method has excellent dispersibility, high heat resistance and electric 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 : Conductive polymer nanomaterials and Polyolefin Preparation of Resin Composite]
Example One
(One) Polyaniline series Preparation of Polymer Microstructure
2 L of distilled water was added to a 5 L reactor and 1.4 mol of hydrochloric acid was added dropwise as a dopant while stirring at 150 rpm, and 1.1 mol of aniline monomer was added dropwise. After stirring for 30 minutes so that the anilinium ions generated by the hydrogen ions dissociated from the hydrochloric acid sufficiently form micelles, 0.53 mole of ammonium persulfate initiator was added dropwise. After about 1 minute, the color of the solution changed from colorless to dark green and polymerization was initiated. After stirring for about 2 hours, 3L of ethanol was poured to complete the reaction, thereby preparing a polyaniline-based polymer microstructure.
(2) Polyaniline series Polymer microstructure Deodorizing
The polyaniline-based polymer microstructure was dispersed again in 1.5 L of distilled water, added with 1.1 moles of ammonium hydroxide, and stirred for about 30 minutes. The excess ammonia water was then washed with ethanol to obtain a polyaniline polymer microstructure that was doped with an acidic dopant.
(3) Production of conductive polymer nanomaterial
The doped polyaniline-based polymer microstructure and the acidic dopant shown in Tables 1 to 2 were mixed and kneaded under the conditions described in Tables 1 to 2 to prepare a conductive polymer nanomaterial.
The conductive polymer nanomaterial was prepared as a pellet having a diameter of 10 mm, and the electrical conductivity was measured by a 4-probe probe method.
(4) Polyolefin Manufacture of Resin Composites
The prepared conductive polymer nanomaterial and the polyethylene resin were kneaded under the conditions shown in Tables 1 and 2 to prepare a polyolefin resin composite material.
(Molar ratio)
Condition
(Molar ratio)
As shown in Tables 1 and 2, the conductive polymer nanomaterial prepared by kneading the polymeric nanomaterial prepared through the doping of the first acidic dopant and the basic compound with the second acidic dopant has a surface resistance value, Dispersed state and surface state, and it was confirmed that the second acidic dopant can be bonded at various molar ratios.
Particularly, it was confirmed that the conductive polymer nanomaterials prepared in Examples 3 to 8 were able to bind to the surface with more than 0.6 molar amount of the acid dopant relative to the monomers used. In addition, the ratio of the acidic dopant to the monomer was 0.7 to 1 mol, It has been confirmed that the conductive polymer nanomaterial having the dopant bonded to the surface has better dispersibility and surface properties and can obtain high conductivity.
Claims (15)
A dedoping step of reacting the polyaniline-based polymer microstructure with a basic compound; And
And kneading the doped polyaniline-based polymer microstructure and the second acidic dopant at a temperature of 40 to 230 DEG C in the absence of a solvent.
(Method for producing conductive polymer nanomaterial).
Wherein the doped polyaniline-based polymer microstructure and the second acidic dopant are kneaded for 10 seconds to 1200 seconds.
Wherein the polyaniline-based polymer microstructure has a diameter of 1 nm to 500 nm.
Wherein the aniline monomer is selected from the group consisting of aniline, alkyl aniline having 1 to 5 carbon atoms, alkoxy aniline having 1 to 5 carbon atoms, dialkoxyaniline having 1 to 5 carbon atoms, sulfonyl aniline, nitroaniline, pyrrole, ethylenedioxythiophene (EDOT) Thiophene, and combinations thereof. 2. The method for producing a conductive polymer nanomaterial according to claim 1,
It said first acid dopant and the second acidic dopant are each sulfonic acid (sulfonic acid), selenite (selenic acid), phosphoric acid, boric acid, hydrogen sulphate (hydrogen sulfate), phosphate Flame (H 3 PO 4), benzene-sulfonic acid (BSA), benzene diisulfonic acid (BDSA), benzethytrisulfonic acid, benzene tetrasulfonic acid (BTSA), benzene peptasulfonic acid (BPSA), hydroxybenzenesulfonic acid (HBSA), hydroxydisulfonic acid, hydroxy (ABSA), camphorsulfonic acid (DBSA), dodecylbenzene disulfonic acid, dodecyl benzene disulfonic acid, alkyl benzene sulfonic acid (ABSA), camphorsulfonic acid At least one compound selected from the group consisting of CSA, p-toluenesulfonic acid (TSA), naphthalenesulfonic acid (NSA), and naphthalene disulfonic acid (NDSA).
Wherein the oxidizing agent comprises at least one selected from the group consisting of persulfate, iodate, chlorate, dichromate, metal chloride and peroxydisulfate.
(Method for producing conductive polymer nanomaterial).
The step of polymerizing the polyaniline-based polymer microstructure by mixing the monomer of the polyaniline-based polymer, the first acidic dopant and the oxidizing agent
Further comprising the step of mixing the monomers of the polyaniline-based polymer, the first acidic dopant, the oxidizing agent, and the compound containing a functional group substituted with at least one amine functional group in the benzene ring.
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) ≪ / RTI >
Wherein the molar ratio of the first acidic dopant to the monomer of the polyaniline-based polymer is from 0.1: 1 to 10: 1.
Wherein the molar ratio of the oxidizing agent to the aniline monomer is 0.1: 1 to 10: 1.
Wherein the molar ratio of the doped polyaniline-based polymer microstructure: the second acidic dopant is 1: 0.1 to 1: 2.
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| KR20190064322A (en) * | 2017-11-30 | 2019-06-10 | 롯데케미칼 주식회사 | Manufacturing method for conductive nano composite resin and conductive nano composite |
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| KR102002723B1 (en) * | 2018-03-23 | 2019-07-22 | 연세대학교 산학협력단 | Preparing method of conductive polymer solution, and conductive polymer film comprising the conductive polymer solution |
| KR20190089576A (en) | 2018-01-23 | 2019-07-31 | 주식회사 파라 | A method for preparing a polyaniline complex for removing antimicrobial and heavy metals in which a polyaniline conductive polymer is doped with an organic acid and a metal ion in a predetermined order, and a polyaniline complex manufactured using thereof |
| KR20200048706A (en) | 2018-10-30 | 2020-05-08 | 주식회사 파라 | Filter using nanoporous polyaniline complex |
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| JP2007224182A (en) | 2006-02-24 | 2007-09-06 | Toyo Ink Mfg Co Ltd | Electrically conductive polymer composition |
Cited By (7)
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| KR20190064322A (en) * | 2017-11-30 | 2019-06-10 | 롯데케미칼 주식회사 | Manufacturing method for conductive nano composite resin and conductive nano composite |
| KR102150151B1 (en) | 2017-11-30 | 2020-08-31 | 롯데케미칼 주식회사 | Manufacturing method for conductive nano composite resin and conductive nano composite |
| KR20190066257A (en) | 2017-12-05 | 2019-06-13 | 주식회사 파라 | A method for preparing a polyaniline complex for removing antimicrobial and heavy metals in which a polyaniline conductive polymer is doped with an organic acid and a metal ion in a predetermined order, and a polyaniline complex manufactured using thereof |
| KR20190089576A (en) | 2018-01-23 | 2019-07-31 | 주식회사 파라 | A method for preparing a polyaniline complex for removing antimicrobial and heavy metals in which a polyaniline conductive polymer is doped with an organic acid and a metal ion in a predetermined order, and a polyaniline complex manufactured using thereof |
| US10829592B2 (en) | 2018-01-23 | 2020-11-10 | Para Co., Ltd. | Method for preparing polyaniline complex with antimicrobial activity and heavy metal removal efficiency using conductive poly aniline polymer doped with organic acid and metal ion in defined order |
| KR102002723B1 (en) * | 2018-03-23 | 2019-07-22 | 연세대학교 산학협력단 | Preparing method of conductive polymer solution, and conductive polymer film comprising the conductive polymer solution |
| KR20200048706A (en) | 2018-10-30 | 2020-05-08 | 주식회사 파라 | Filter using nanoporous polyaniline complex |
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