KR101053071B1 - Preparation methods of polyanilines with high yields - Google Patents
Preparation methods of polyanilines with high yields Download PDFInfo
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- KR101053071B1 KR101053071B1 KR1020100129606A KR20100129606A KR101053071B1 KR 101053071 B1 KR101053071 B1 KR 101053071B1 KR 1020100129606 A KR1020100129606 A KR 1020100129606A KR 20100129606 A KR20100129606 A KR 20100129606A KR 101053071 B1 KR101053071 B1 KR 101053071B1
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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
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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
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
Abstract
Description
The present invention relates to a method for producing high yielding granular conductive polymers, and more particularly, a needle-like polyaniline synthesized by adding a dopont to at least one monomer selected from aniline, pyrrole and thiophene, and then adding an oxidant In the method of producing a large amount of granular conductive polymers in high yield, characterized in that the granular conductive polymer mixed with acicular and spherical conductive polymers are prepared by repeating the polymerization again by using the filtrate obtained in washing. It is about.
In general, polyaniline is a conductive polymer that is relatively stable, easily doped with strong acids, and is more economically competitive than other conductive polymers at a relatively low price (OT Ikkala, J. La, K. Vakiparta, E. Virtanen. H.). Ruohonen, H. Jarvinen, T. Taka, P. Passiniemi, Y. Cao.A. Andreatta, P. Smith, AJ Heeger, Synth.Met., 69, 97, 1995). The density is known as 1.329 g / cm 3 (J. Stejskal, RG Gilbert, Pure. Appl. Chem., 74, 857, 2002). In addition, the weak processability and solubility, which are pointed out as disadvantages, are improved by using various dopants.
Aniline polymerization is an oxidation polymerization that proceeds in aqueous solution with dopants and oxidants. Dopants are used to promote the activation required to remove electrons from aniline, and oxidants are added to absorb electrons and remove protons. Theoretically, the aniline, the dopant and the oxidant are added to each other in an equimolar ratio, but the molar ratio is arbitrarily adjusted according to the target conductivity and the economical efficiency of the material, and sufficient stirring is performed at each reaction temperature to form the aniline-dopant composite. As reported by Y. Haba et al. (Synth. Met., 106, 59, 1999), the aniline-dodecylbenzenesulfonic acid complexes showed a needle-like shape at room temperature, but when the reaction temperature was lowered to 0 degrees, the needle-like polyaniline was finally obtained. Cannot be synthesized. The oxidation polymerization system of aniline is not known exactly, and the reaction systems of other aromatic conductive polymers such as polyphenylene and polyoxyphenylene are not reported for the same reason. Aniline oxidation polymerization proceeds by removing two protons and electrons from one aniline monomer in which one oxidant is present as a dopant complex (Scheme 1).
One peroxide sulfate from one ammonium persulfate (APS) turns into two sulfite ions, absorbing two electrons and protons. The rate of oxidant addition is known to affect the exothermic reaction of the oxidative polymerization and the particle morphology of polyaniline (Y. Cao et al., Polymer , 30 , 2305, 1989).
In the above, sulfite ions remain in the filtrate, which can be recycled back into the reaction medium, thereby increasing the yield of the conductive polymer by entering the inside of the conductive polymer synthesized together, forming a complex with aniline while functioning as an auxiliary dopant. This point has been made to the inventor.
On the other hand, aniline oxidation polymerization begins with the coupling between resonance stabilized aniline cation radicals as proposed by Y. Wei et al . ( J. Phys. Chem. , 94 , 7716, 1990) (Scheme 2). The aniline dimer growth ends are changed to trimers and tetramers, and polymerization continues until the polyaniline growth chain loses motility. The polyaniline is fully oxidized to phenyganiline and then partially reduced to complete the reaction with emeraldine. The total reaction time is about 6 minutes after the last oxidizer is added. The general feature of spherical polyaniline in the form of ordinary polyaniline is that it polymerizes at low reaction temperatures close to zero degrees and fast oxidant addition rates of about 30 minutes. (S. Davied, YF Nicolau, F. Melis, A. Revillon, Synth. Met., 69, 125, 1995).
Scheme 2
On the other hand, the yield of the conventional polyaniline synthesis is generally increased by the amount of oxidizing agent, but about 30% on an equimolar basis, the production cost of polyaniline is high and the shape is spherical, so it is known that its use as a conductive filler is limited due to its cohesion. (Y. Cao et al., Polymer , 30 , 2305, 1989).
On the other hand, the conductive polymer has a difference in physical properties according to its shape, the general physical properties are shown in Table 1 below.
In the test of the granular polyaniline / thermoplastic polyurethane (TPU4003, Bayer) adhesive by the present inventors, the filling amount until the resistance reaches 10 5 Ω / cm 2 is from about 25% by weight, and granular / acicular (1/1) The mixed polyaniline was from about 15% by weight, and the acicular polyaniline was from about 10% by weight (Table 1). Dispersibility and particle stability of the base polymer were poor in granular polyaniline, and acicular polyaniline was best. The extent of surface release in the adhesive is relatively poor in granular polyaniline, acicular polyaniline is common, and granular / acicular polyaniline is in between. The finish and dyeability are worst with granular polyaniline and acicular polyaniline is common. Overall, granular polyaniline is a low-cost, low-performance material, acicular polyaniline is the highest-performance conductive filler, and granular / spheroidal polyaniline has a moderate price and performance.
The application of polyaniline is largely similar to that of other electrically conductive fillers, namely carbon black, carbon five and carbon nanotubes. For example, electromagnetic shielding (resistance required is about 10 5 -10 6 Ω / cm 2 ), microwave shielding material, electrostatic discharge material (required resistance is 10 6 -10 9 Ω / cm 2 ), for biosensing Electrodes, light emission diodes, lithium polymer secondary battery electrodes (10 5 Ω / cm 2 or less), antirust materials, and the like. Forms produced by melt processing are transparent and translucent films, plate-like (Y. Cao, P. Smith, AJ Heeger, Synth. Met., 55-57, 3514, 1993), cable cladding (SJ Davis, TG Ryan, CJ Wilde, G. Beyer, Synth.Met., 69, 209, 1995), coating materials (OT Ikkala, J. Laakso, K. Vakiparta, E. Viranen, H. Ruohonen, H. Jarvinen, T. Taka , P. Passinenmi, Y. Cao, A. Andreatta, P. Smith, AJ Heeger, Synth.Met., 69, 97, 1995).
The present invention improves the weak dispersion and high self-cohesion when the common conductive polymer particles are mixed with other base polymers, while improving the area ratio of the conductive polymer to improve the dispersion yield in the base polymer resin to solve the low yield of the conductive polymer. An object of the present invention is to propose a method for synthesizing rod-like polyaniline, which is a mixture of acicular and spherical shapes, so as to reduce the content of conductive fillers by increasing self-cohesion.
After studying the above point, the present inventor first reacts at least one monomer selected from dopant, aniline, pyrrole and thiophene in an aqueous solution first under appropriate reaction conditions, and recycles the filtrate after the first reaction. Once polymerized, the remaining dopants and oxidant by-products reacted in the first synthesis step can be used in the second synthesis step to obtain economically obtained granular conductive polymers in which acicular and spherical conductive polymers are properly mixed. The present invention has been made in light of this.
In summary, the method of the present invention provides a method for producing granular conductive polymers in which novel and advanced needle and spherical conductive polymers are mixed.
The method of the present invention comprises the first step of oxidatively polymerizing at least one monomer selected from paratoluenesulfonic acid and aniline, pyrrole and thiophene in an aqueous solution at a reaction temperature of 5 to 15 ° C. for 2 to 4 hours to synthesize conductive polymers; and the first step A second step of filtering the conductive polymer synthesized in the step; and one or more monomers selected from paratoluenesulfonic acid, aniline, pyrrole, and thiophene in the remaining filtrate after filtering the conductive polymer in the second step in an aqueous solution at a reaction temperature of 5 to 5 And a third step of synthesizing the conductive polymer by oxidative polymerization at 15 ° C. for 2 to 4 hours. The method may include repeatedly performing the second and third steps after the third step as necessary. do.
Here, the oxidizing agent used in the oxidation polymerization may be at least one selected from the group consisting of ammonium peroxide sulfate, K 2 Cr 3 O 7 , KIO 3 , FeCl 3 , KMnO 4 , KBrO 3 , KClO 3 .
According to the above method of the present invention, 1) improving the yield of the conductive polymer by recycling the filtrate, and 2) obtaining a granular conductive polymer (homopolymer or copolymer) in which acicular and spherical conductive polymers are properly blended. Will be.
The conductive polymer (monomer) of the present invention is at least one selected from aniline, pyrrole and thiophene, but polyaniline, which is a representative conductive polymer for convenience of explanation, will be described.
According to the inventors' discovery, unreacted aniline and residual dopant contained in the reaction solution of acicular polyaniline obtained by doping aniline with p-toulenesulfonic acid (pTSA) and synthesized by using ammonia peroxide sulfate as an oxidizing agent at low temperature The reaction yield can be improved by repeatedly synthesizing phosphorus para-toluenesulfonic acid and byproducts of oxidants sulfite ions with dopants under the same conditions as used for synthesizing acicular polyaniline.
According to the experiments of the present inventors (described above) in the electrically conductive adhesive prepared by processing the solution of the conductive polymer (see Table 1), spherical particles and needles having an aspect ratio (L / D) of 1-10 By using polyaniline of granular particles composed of granular particles, dispersion is better in the thermoplastic base resin than in the case of using the conventional carbon black, and sufficient thermal stability can be obtained under the processing conditions (maximum operating temperature of 200 ° C), and the reinforcing effect of the base material is obtained. In addition, it was found that the use of conductive materials can be reduced by lowering the electrically conductive through concentration (25 wt%), which can eventually replace the use of environmentally harmful carbon black.
The present invention is suitable for mass production of granular polyaniline, has electrical properties similar to those of metals, and has the characteristics of high molecular properties and can be easily processed.
In addition, it can control electric conductivity, mechanical properties, production cost and processing characteristics while accommodating static electricity dissipation capacity.
In addition, the polymer according to the method of the present invention is easier to handle and process than carbon black, and has high affinity with the base polymer during processing, thereby obtaining excellent mechanical properties, similar to the production cost of conductive carbon black, and It has the effect of lower raw material and processing cost than carbon nanotubes.
The granular conductive polymer produced according to the present invention is processed into a film, a plate, a protective layer and a coating, and used as a conductive filler for electromagnetic wave, radio wave, microwave shielding material and electrostatic dispersing material, electrode material of various sensors, light emitting device and It is expected that the application range of the secondary battery electrode and the antirust material can be widely applied.
1 is a diagram showing the synthesis of acicular polyaniline.
Figure 2 is an electron micrograph of the (A) spherical, (B) single-wall needle and (C) multi-wall needle polyaniline particles synthesized according to the method of the present invention.
3 is an electron micrograph of granular polyaniline synthesized according to the method of the present invention.
4 is a schematic process diagram for producing granular polyaniline synthesized according to the method of the present invention.
5 is a graph of surface resistance and electrical conductivity of acicular polyaniline according to the molar concentration of aniline.
6 is a graph showing the surface resistance of acicular polyaniline and granular polyaniline and carbon black synthesized according to the method of the present invention according to the conductive filler content.
Hereinafter, the method of the present invention will be understood more specifically by the description of the following examples.
The present invention relates to a large-scale manufacturing method of granular electrically conductive polymers composed of acicular and spherical particles synthesized through a relatively high reaction temperature (5 to 15 degrees) and a long oxidizer addition time (2 to 4 hours).
The oxidants and dopants used in the examples were ammonium peroxide sulfate and paratoluenesulfonic acid. The optimum reaction temperature was about 5 to 15 degrees, and the optimum oxidant addition time was changed depending on the aniline molar concentration from 2 to 4 hours. When the addition time of the oxidizing agent was within 2 hours, spherical particles were developed, and when 4 hours or more, spheroidal particles were destroyed, and many spherical particles were produced. Needle-shaped particles were synthesized from needle-shaped aniline complexes formed by complexing of aniline and dopant in aqueous solution at room temperature, and aniline complexes correspond to reaction temperatures ranging from 5 to 15 degrees and corresponding to 2 to 4 hours. Through the addition of the oxidizing agent, the polymerization was carried out while maintaining the needle shape in various forms to obtain acicular polyaniline. At this time (yield 0), the yield was about 37% and the electrical resistance was about 4.7 Ω / cm 2 (Table 2). When the reaction temperature is 5 degrees or less, the spherical particles are predominantly synthesized. When the reaction temperature is 15 degrees or more, the spherical particles are destroyed and the number of spherical particles is also dominant. In the next reaction (reaction order 1), the filtrate recovered from the previous reaction was reused as a reaction medium, and the reaction was carried out under the same reaction conditions. The filtrate contains unreacted aniline, residual pTSA, and sulfite ions, a degradation product of the oxidant. The acidity of the filtrate recovered at
TABLE 2
Hereinafter, a method for producing granular polyaniline of high yield according to the present invention will be described in detail with reference to the accompanying drawings.
1 is a diagram schematically showing the synthesis of acicular polyaniline of the present invention. The average diameter is 8 microns and is usually synthesized polyaniline particles with pTSA, a dopant inside, and a polyaniline layer formed on the outside, covering the inner dopant core like a shell.
The synthesis process is as follows. The polyaniline is synthesized by an inverse emulsion polymerization in which the dopant acts as an emulsifier to form micelles in aqueous solution and the aniline monomer added to the surface of the micelle composed of the dopant is polymerized by the oxidant. . At this time, the structure of the dopant located in the inner core (core) plays an important role in the shape of the particles. The polyaniline / dopant composites varied in particle shape with temperature and oxidant addition time, and needle-like polyaniline / dopont complexes were observed at reaction temperature of 5-15 degrees and oxidant addition time of about 2-4 hours. Single wall acicular polyaniline was synthesized at an oxidant addition time of 2.5-3 hours, and multiwall acicular polyaniline was synthesized at 3.4-4 hours. Single wall acicular conductivity was about 4.7 Ω / cm 2 and slightly higher than that of multi-wall acicular polyaniline (about 7 Ω / cm 2 ). The high yield granular polyaniline synthesized by the present invention is composed of a mixture of spherical and single-walled polyaniline.
Figure 2 is an electron micrograph of the (A) spherical, (B) single-wall needle and (C) multi-wall needle polyaniline particles that are components of the aniline polymer synthesized by the method of the present invention. The average diameter of single-wall acicular polyaniline is 8 microns, the average length is 100 microns, and it grows from spherical particles at the reaction temperature of 15 degrees and 2.5-3 hours, and the area ratio is 18-25. The conductivity was increased due to the increase in crystallinity and obtained up to 3 S / cm. Multi-wall acicular polyaniline is a conjugate of single-wall acicular polyaniline and has a smaller area ratio and conductivity than single-wall acicular polyaniline.
3 is an electron micrograph of granular polyaniline synthesized by the method of the present invention. Granular polyaniline composed of spherical and acicular particles had the intermediate properties of spherical and acicular polyaniline in terms of filling amount. The electrical conductivity penetrating concentrations of carbon black and acicular polyaniline were 35 and 15 wt%, and in the case of granular polyaniline, the electrical resistance reached 10 4 Ω / cm 2 at 25 wt% or more. The yield of granular polyaniline improved from the third order of reaction to 97 wt% on average. The electrical resistance was similar to acicular polyaniline (Tables 1 and 2).
4 is a schematic process diagram for producing granular polyaniline synthesized by the process of the present invention. As paratoluenesulfonic acid is dissolved in water in the main reactor, the reactor temperature is lowered to 15 degrees with a coolant. The aniline stored in the auxiliary reactor at the stirring speed of 1300 rpm is slowly introduced into the main reactor over 1 hour. In another auxiliary reactor, ammonium peroxide sulfate is dissolved in water and slowly added over 3 hours. At this time, the stirring speed was lowered to 1100 rpm. After all the APS was introduced into the main reactor, after 3 hours, the product in the main reactor was poured into the filter and filtered, and the filter was placed in a dryer and completely dried at 70 degrees. Package product after drying (order 0). The yield is then about 37% by weight. The reaction is restarted by placing the filtrate back into the main reactor for the next reaction (reaction order 1). From the third order, the yield is increased to about 97% by weight.
5 is a surface resistance and electrical conductivity of acicular polyaniline according to the aniline molar concentration. The higher the aniline molar concentration, the smaller the amount of water used, and thus the reactor size can be reduced, and since the filtrate is totally recycled during the synthesis of granular polyaniline, no waste water remains, but the waste water can be reduced during the final order reaction. have. The surface resistance of acicular polyaniline synthesized at aniline concentration of 0.4 M was about 23 Ω / cm 2 , and as the aniline concentration increased, the surface resistance decreased little by little, and the electrical conductivity increased inversely. It increased with increasing concentration. At aniline concentration of 0.7 M, the surface resistance was about 4.7 Ω / cm 2 . In order to prepare high yield granular polyaniline of the present invention, water was used using aniline concentration of 7M reaction conditions with a minimum amount of use.
6 is a diagram showing the surface resistance of acicular polyaniline and granular polyaniline and carbon black synthesized by the method of the present invention according to the conductive filler content. Each conductive filler was added to a solution made by dissolving thermoplastic polyurethane (TPU4003, Bayer) in acetone / ethyl acetate (1/1) at a solid content of 10% by weight, and then a film about 0.1 mm thick on a polyethylene terephthalate film. After making the surface resistance of the film was measured. Acicular polyaniline reached a surface resistance of 10 4 Ω / cm 2 at 15% by weight, granular polyaniline synthesized by the method of the present invention from 25% by weight, and carbon black at 40% by weight.
Example 1 Acicular Polyaniline Synthesis (0 Reaction Order)
90 grams (1 mole) of paratoluenesulfonic acid was dissolved in 1000 ml water in a 5 L reactor. The cooling reactor was filled with coolant, and the reaction temperature was controlled to an accuracy of W 0.1 with a heat generator and a cooler. 93 g (1 mol) of aniline was slowly added to the reactor over 1 hour at a stirring speed of 1300 rpm to form aniline / paratoluenesulfonic acid complex. The polymerization was initiated with the addition of 228 grams (1 mol) of ammonium peroxide sulfate solution dissolved in 428 ml water at a very slow rate at 2.4 ml / min (3 hours). The reaction temperature was 15 degrees and the aniline molar concentration was 0.7 mol. The precipitate was washed through filtration to remove the remaining unreacted material after 3 hours of reaction time. Yield, electrical resistance and maximum area ratio were 37% (by weight including aniline, paratoluenesulfonic acid and ammonium persulfate), 4.7 Ω / cm 2 and 20 L / D, respectively.
Example 2: Granular Polyaniline Synthesis (Reaction Order 1)
The polymerization method was the same as in Example 1, but the filtrate (about 1000 mL) recovered in Example 1 (reaction order 0) was used as a solution for dissolving paratoluenesulfonic acid. The acidity of the filtrate was an average pH of 0.5, the yield of polyaniline was an average of 80%, the surface resistance was about 4.5 Ω / cm 2 .
Example 3: Granular Polyaniline Synthesis (Reaction Order 2)
The polymerization method was the same as in Example 1, but the filtrate (about 1000 mL) recovered in Example 2 (reaction order 1) was used as a solution for dissolving paratoluenesulfonic acid. The acidity of the filtrate was an average pH of 0.4, the average yield of polyaniline was 70%, the average surface resistance was 4.5 Ω / cm 2 .
Example 4 Granular Polyaniline Synthesis (Reaction Order 3)
The polymerization method was the same as in Example 1, but the filtrate (about 1000 mL) recovered in Example 3 (reaction order 2) was used as a solution for dissolving paratoluenesulfonic acid. The acidity of the filtrate was an average pH of 0.5, the average yield of polyaniline was 101%, the average surface resistance was 5.6 Ω / cm 2 .
Example 5 Granular Polyaniline Synthesis (Reaction Order 4)
The polymerization method was the same as in Example 1, but the filtrate (about 1000 mL) recovered in Example 4 (reaction order 3) was used as a solution for dissolving paratoluenesulfonic acid. The acidity of the filtrate was pH -0.3, the average yield of polyaniline was 97%, and the surface resistance was 4.5 Ω / cm 2 .
Example 6 Synthesis of Granular Polyaniline (Reaction Order 5)
The polymerization method was the same as in Example 1, but the filtrate (about 1000 mL) recovered in Example 5 (reaction order 4) was used as a solution for dissolving paratoluenesulfonic acid. The acidity of the filtrate was pH -0.3, the average yield of polyaniline was 95%, and the average surface resistance was 4.7 Ω / cm 2 .
Example 7 Preparation of Acicular Polyaniline / TPU4003 Conductive Adhesive
After 30 g of TPU4003 was completely dissolved in acetone / ethyl acetate (135 g / 135 g) by stirring in a 3 L reactor, the acicular polyaniline content prepared in Example 1 was adjusted to 5, 10, 15, 20, Polyaniline / TPU4003 adhesives were prepared at 25, 30, 35 and 40 weight percent. The conductive adhesive was prepared on the average film of 0.1 mm thick PET film on the surface resistance was measured.
Example 8 Preparation of Granular Polyaniline / TPU Conductive Adhesive
After 30 g of TPU4003 was completely dissolved in acetone / ethyl acetate (135 g / 135 g) by stirring in a 3 L reactor, the granular polyaniline content prepared in Example 2-6 was adjusted to adjust 5, 10, 15, Polyaniline / TPU4003 adhesives were prepared at 20, 25, 30, 35 and 40 weight percent. The conductive adhesive was prepared on the average film of 0.1 mm thick PET film on the surface resistance was measured.
Comparative Example 1: Preparation of Carbon Black / TPU Conductive Adhesive
The preparation method was the same as in Example 7, except that carbon black (Mitsubishi MA100) was used instead of acicular polyaniline.
Comparative Example 2: Synthesis of Spherical Polyaniline
Spherical polyaniline was the same as that of Example 1 as a normal polyaniline, but was polymerized at a low reaction temperature close to 0 degrees and a rapid oxidizing agent addition rate of about 30 minutes.
The method of the present invention can produce a large amount of granular polyaniline as shown in Examples 1 to 6 above, and is expected to replace carbon black due to its low production cost and performance as an excellent conductive filler. It is expected to replace the carbon black adhesive of Comparative Example 1 due to the excellent physical properties of the electrically conductive adhesives prepared in Examples 7 and 8, and as an electromagnetic shielding material for interior floors, barriers, mobile phones, computer monitors, TV exteriors and various electronic products. It is expected to be used as a conductive coating of. In addition, it is expected that the scope of application will be widely applied, such as electrostatic absorbing plates, antirust and radar absorbing resins, and polymer secondary battery anodes (K. Ghanbari, et al., Journal of power sources, 170, 513, 2007). .
Claims (2)
A first step of oxidatively polymerizing at least one monomer selected from paratoluenesulfonic acid, aniline, pyrrole and thiophene in an aqueous solution at a reaction temperature of 5 to 15 ° C. for 2 to 4 hours to synthesize conductive polymers;
A second step of filtering the conductive polymer synthesized in the first step;
The conductive polymer was filtered in the second step, and the remaining filtrate was synthesized by oxidizing and polymerizing at least one monomer selected from paratoluenesulfonic acid, aniline, pyrrole and thiophene in an aqueous solution at a reaction temperature of 5 to 15 ° C. for 2 to 4 hours. A third step of the; manufacturing method of the granular conductive polymer comprising a.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030082059A (en) * | 2002-04-16 | 2003-10-22 | 주식회사 옴니켐 | Novel process of polyaniline |
| KR20040073183A (en) * | 2003-02-13 | 2004-08-19 | 주식회사 금강고려화학 | Water-soluble conductive polymer composite, preparing method thereof, and antistatic coating composition containing the same |
| KR100850482B1 (en) | 2007-03-29 | 2008-08-05 | 한양대학교 산학협력단 | Method of preparing nano-structure of conductive polymer and nano-structure prepared thereby |
| KR20090079820A (en) * | 2008-01-17 | 2009-07-22 | 이성주 | Soluble Conducting Polymers and Fabrication Methods of the Same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030082059A (en) * | 2002-04-16 | 2003-10-22 | 주식회사 옴니켐 | Novel process of polyaniline |
| KR20040073183A (en) * | 2003-02-13 | 2004-08-19 | 주식회사 금강고려화학 | Water-soluble conductive polymer composite, preparing method thereof, and antistatic coating composition containing the same |
| KR100850482B1 (en) | 2007-03-29 | 2008-08-05 | 한양대학교 산학협력단 | Method of preparing nano-structure of conductive polymer and nano-structure prepared thereby |
| KR20090079820A (en) * | 2008-01-17 | 2009-07-22 | 이성주 | Soluble Conducting Polymers and Fabrication Methods of the Same |
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