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J. Stejskal and I. Sapurina
Abstract Polyaniline, a conducting polymer, is prepared by the oxidation of aniline hydrochloride with ammonium peroxodisulfate in aqueous medium. The polymer is obtained in nearly quantitative yield; its conductivity at 20°C is 4.4 Scm–1. Protonated polyaniline is converted to non-conducting polyaniline base by treatment with ammonium hydroxide solution.
Form: Function: Preparation: Composition: polymer powder conducting polymer oxidative polymerization [C24H18N4]n 2n acid
Conducting polymers have received ever-increasing attention, especially in last two decades. Among them, polyaniline (PANI) is popular for its ease of preparation, good level of electrical conductivity, and environmental stability.[2–8] It is prepared by the oxidative polymerization of aniline with a suitable oxidant, e.g., ammonium peroxodisulfate. The synthesis uses common chemicals and proceeds in acidic aqueous medium at ambient temperature and atmosphere. The polymer is produced within a few minutes as a precipitate and thus easily collected by filtration at virtually quantitative yield. Polyaniline exists in a variety of forms that differ in chemical and physical properties.[1–8] The most common form, green protonated emeraldine (Fig. 1), has a conductivity on a semiconductor level in the order of 100 S cm–1, many orders of magnitude higher than that of common polymers (<10–9 S cm–1) but lower than that of typical metals (>104 S cm–1). Protonated PANI, so-called PANI "salt", e.g., PANI hydrochloride, converts to the non-conducting blue emeraldine base when treated with a base [5,9] (Fig. 1), such as ammonium hydroxide.
A– is an anion. endowing them with new electrical. sensors. The preparation of PANI has recently been investigated within the collaborative project carried out by a task group of the International Union of Pure and Applied Chemistry. Stejskal and I. Sapurina NH NH A NH NH A Protonated polyaniline (emeraldine) -2H A deprotonation NH Polyaniline (emeraldine) base NH N N Fig. and actuators...g. e. membranes. and porous substrates. The information provided here is based on the results and experience gained during that study. Conducting polymers have been used in the design of new catalysts for organic syntheses. and surface properties.11] The changes in the physicochemical properties of PANI occurring in response to various external stimuli are used in various applications.g. used as received. used as received. fibers. like the development of “plastic” microelectronics and “smart” fabrics. chloride. in electrodes. . The follow-up project concerned the preparation of colloidal PANI dispersions and in-situ polymerized thin films. Acetone. The preparation of PANI colloids is one of the ways to cope with the difficult processibility of conducting polymers. chemical. Polyaniline (emeraldine) salt is deprotonated in alkaline medium to polyaniline (emeraldine) base. Surface coating with conducting polymers can modify adsorption phenomena and therefore be used in the separation science. e. textiles. 1. Some uses are based on the combination of electrical properties typical of semiconductors with materials parameters characteristic of polymers. Ammonium peroxodisulfate.200 J. Polyaniline is used as a filler in the preparation of conducting composites. purum. powders.[10. and for the surface modification of microparticles. used as received. Ammonium hydroxide solution (2–3 %). purum.  Materials Aniline hydrochloride.
Both solutions are mixed at room temperature (~18–24°C) in a beaker. A.2 M aniline hydrochloride with 0. The average yield of PANI hydrochloride is 2. and similarly with acetone. Ammonium peroxodisulfate (5. here PANI hydrochloride. the green emeraldine form of PANI (4) (Fig. At the end of polymerization. Aniline hydrochloride (2. Mechanism of the Aniline Polymerization The aniline hydrochloride. the pernigraniline is reduced with residual aniline to the final product. and left at rest or at gentle stirring to polymerize.71 g. or generally any aniline salt (1). the mixture is left to cool down for several hours. can result in the overheating of the system. Polymerization using aniline concentrations over 1 M. 25 mmol) is similarly dissolved in water also to 50 ml of solution. the formation of the protonated pernigraniline intermediate (3) (Fig.Polyaniline – A Conducting Polymer 201 Safety and Disposal The oxidation of aniline is exothermic.2M HCl. washed with three 100 ml portions of 0. After the polymerization has been completed in about 10 min. Such reaction conditions should be avoided. Preparation of Polyaniline Hydrochloride The preparation of protonated PANI. Procedures The polymerization of aniline reported here was designed to be as simple as possible. is oxidized at first to the aniline cation radical (2) (Fig. the ammonium peroxodisulfate is reduced to ammonium sulfate (Fig. 2d). is based on the oxidation of 0. During the reaction. 2c). 2b) is observed during the polymerization and manifested by the deep blue color of the reaction mixture. Summing all reaction .5 l).25 M ammonium peroxodisulfate in aqueous medium. 20 mmol) is dissolved in distilled water in a volumetric flask to 50 ml of solution. followed by an explosion. The synthesis is based on mixing aqueous solutions of aniline hydrochloride and ammonium peroxodisulfate at room temperature. Although the detailed reaction mechanism of aniline polymerization is not fully understood. 2a). The PANI precipitate is collected on a filter. Polyaniline (emeraldine) powder is dried in air and then in vacuo. especially when carried out in large volumes (over 0. followed by the separation of PANI hydrochloride precipitate by filtration and drying.59 g.13 g (98%).
25 is found. The course of polymerization can also be followed by changes in . 2.A b 8H 8e NH A NH A 3 NH A NH A c 2A +2e NH A NH 4 NH A NH d 5 (NH4)2S2O8 + 10 H + 10 e 5 (NH4)2SO4 + 5 H2SO4 4 NH2. the temperature increases. the temperature stays virtually constant. Sapurina steps ( ).HA + 5 (NH4)2S2O8 NH A NH NH A NH + 5 (NH4)2SO4 + 5 H2SO4 + 2 HA Fig. During the induction period. Stejskal and I.202 J. the color of the mixture turns to deep blue. Once the polymerization has started.HA 4H 4e 4 2 NH2. a 4 1 NH2.25 M. respectively. This is why the concentrations of aniline hydrochloride and ammonium peroxodisulfate were selected in the present protocol as 0. the stoichiometric oxidant/monomer ratio 5/4 = 1. the reaction mixture becomes blue as oligomeric intermediates are produced. 3).2 M and 0. Oxidation of an aniline salt by ammonium peroxodisulfate to yield protonated polyaniline (emeraldine) hydrochloride. The surface of the reaction vessels acquires a metallic tint due to a PANI coating.15] (Fig. and the consistency becomes that of a slurry. HA is any acid. The oxidation of aniline is exothermic and can conveniently be followed by the temperature changes [13.
 Polyaniline nanotubes are obtained when the oxidation of aniline takes place in the solution of weak acids. (3) Various inorganic and organic acids at various concentrations can be used instead of hydrochloric acid in the polymerization of aniline. 3. Subsequent rinsing with ace- . 2). accelerated by traces of various compounds. Fig. Temperature profile in the polymerization of aniline (0.Polyaniline – A Conducting Polymer 203 the acidity because protons (sulfuric acid) are produced during the polymerization (Fig. This means that the PANI is partly protonated also by this acid. such as acetic acid [18. The course of the polymerization is. Polyaniline is produced as fused nanogranules. however.  (4) When using ammonium peroxodisulfate as an oxidant. sulfuric acid is produced during the polymerization (Fig. 2). The electrical and material properties of PANI vary correspondingly. Washing of PANI with hydrochloric acid after the preparation should replace most of the sulfate counter-ions with chloride and the resulting product is thus PANI hydrochloride.2 M aniline hydrochloride oxidized with 0.25 M ammonium peroxodisulfate in 100 ml of aqueous medium).19] or in water. Comments (1) The purity of the chemicals is not crucial as far as the yield and properties of PANI are concerned. (2) An equimolar mixture of aniline and hydrochloric acid can be used instead of aniline hydrochloride. The presence of excess (1 M) hydrochloric acid in the reaction mixture improves the conductivity of PANI.
washed with the solution of ammonium hydroxide.5 a Based on the formulae shown in Fig.a 66.5 5. The reaction of the supernatant liquid must be alkaline.2 4. Preparation of Polyaniline Base Polyaniline hydrochloride is placed in a beaker and excess of ca 2–3% aqueous ammonium hydroxide is poured over the powder.204 J.a 79. Drying PANI precipitate while it still contains water produces polymer lumps. The relative proportion of carbon and nitrogen in the PANI base is thus increased.9 10.1 1.0 Calcd. at the expense of the lower content of . Characterization Elemental composition: The chlorine content reflects the protonation in PANI hydrochloride (Table 1).0 13. 1.7 4.9 16. (6) All surfaces in contact with the reaction mixture become coated with a thin (~200 nm) PANI film.[13. below -10°C.25] This fact can be used for the coating of various materials with a PANI overlayer. The color of the greenish PANI hydrochloride changes to blue after neutralization (Fig. The thus produced PANI has a higher molecular weight. Sapurina tone is needed to obtain PANI as a powder. Polyaniline base is collected on the filter.[14.0 5. but its conductivity is improved only marginally. The polymerization is often carried out in an ice bath (0–2°C).[22. Elemental composition of polyaniline  Sample %C %H %N % Cl %S Polyaniline hydrochloride Found 59.3 Calcd.0 15. which may be difficult to process further. Stejskal and I.9 0.3 Polyaniline base (after deprotonation of polyaniline hydrochloride) Found 75.23] and proceeds even at -50°C.[26-28] B.6 0. the presence of sulfur corresponds to a partial incorporation of residual sulfate or hydrogen sulfate anions produced by the reduction of peroxodisulfate during polymerization (Fig. Table 1. (5) The polymerization of aniline can be carried out at both higher and lower temperatures. 2). and then dried. 1). followed by acetone.6 11. 1). Hydrochloric acid is removed from the PANI hydrochloride after deprotonation with ammonium hydroxide (Fig.6 12.  The reaction is then much slower and takes several days.21] The polymerization can be carried out in the frozen reaction mixture.
The band at 1144 cm–1 can be assigned to a vibration mode of a protonated imine group. 4.027 g cm–3 at 20 °C and that of PANI base 1. indicating partial substitution of the phenyl rings with chlorine. The molar mass distribution is relatively broad.[32. Molar mass: The mass-averaged molar mass of PANI base determined by gel permeation chromatography in N-methylpyrrolidone by using the polystyrene calibration is Mw = 58 100 g mol–1 (Fig.006 g cm–3.245 ± 0. The absorption at 1302 cm–1 corresponds to -electron delocalization induced in the polymers by protonation  and is reduced after the deprotonation. the mass-to-number molar-mass ratio being Mw/Mn = 3.3. Fig. These are blue-shifted to 1590 cm–1 and 1500 cm–1 after deprotonation to PANI base.[31. a value common for the many polymers met in practice.329 ± 0.32] The band at 1374 cm–1. Infra-red spectra of polyaniline hydrochloride and polyaniline base dispersed in potassium bromide pellets. The band characteristic of the conducting protonated form is found at about 1245 cm–1.34-36] The aromatic-ring and out-of-plane C–H deformation vibrations manifest themselves in the region of 900–700 cm–1. is present in the spectrum of PANI base but absent from the spectrum of PANI hydrochloride. 5). which is characteristic of the conducting form of PANI [29.30]. It overlaps the band of in-plane C–H deformation vibrations at 1164 cm–1 observed in PANI base. Typical peaks in the infrared spectra of PANI hydrochloride. are observed at 1569 cm–1 and 1480 cm–1 (Fig. 4).Polyaniline – A Conducting Polymer 205 chlorine. This is the value corresponding to a degree of polymerization of about 640 aniline units. Sulfonation of the phenyl rings is responsible for the presence of sulfur in the PANI base. associated with C–N stretching in the neighborhood of a quinonoid ring. Some chlorine remains in the PANI base even after deprotonation. . Density: The average density of PANI hydrochloride is 1. corresponding to quinone and phenyl ring deformations. FTIR spectra: The infrared spectrum of PANI hydrochloride shows a broad absorption at wavenumbers >2000 cm-1.
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