A NEW METHOD ON THE CHEMICAL SYNTHESIS OF DOPED POLYPYRROLE INITIATED BY CuCl_2-C_2H_5OH SYSTEM

Our objectives were to develop a new chemical method for the polymerization of pyrrole. CuCl_2 dissolved in C_2H_5OH solvent is primarily used for the initiation polymerization of pyrrole. The polymers with different yield and conductivity were obtained by raring the initial concentration of Cu~(2+). The initial concentrations of Cu~(2+) varied from 1.2 ×10~(-4) mole to 6.48 ×10~(-3) mole Cu~(2+) with 2.16 ×10~(-2) mole pyrrole. The polypyrrole obtained was characterized with elemental analyzer, XPS, IR spectroscopy, Four-point probe and SEM.     

Synthesis and Characterization of Polyvinylferrocene/Polypyrrole Composites

Conducting polymer composites of polyvinylferrocene and polypyrrole (PVF/PPy) were synthesized chemically by the in situ polymerization of pyrrole in the presence of PVF using FeCl₃ as oxidant. Acetic (CH₃COOH) and boric (H₃BO₃) acids were used as the synthesis medium. Effects of the synthesis medium on the properties of the PVF/PPy composite were investigated. The PVF/PPy composites and homopolymers were characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and magnetic susceptibility techniques. Conductivity measurements were performed using the four‐probe technique. We found that the conductivities of PVF/PPy‐H₃BO₃ (1.19 S cm^?1) and PVF/PPy‐CH₃COOH (4.5×10^?1 S cm^?1) increased relative to those of the homopolymers of PPy‐H₃BO₃ (2.1×10^?2 S cm^?1) and PPy‐CH₃COOH (1.2×10^?2 S cm^?1) due to the interaction of PVF with the pyrrole moiety. The stability of all homopolymers and composites were investigated by thermogravimetric analysis and by conductivity measurements during heating‐cooling cycles. There was a small drop in conductivity caused by the annealing of PVF/PPy composites at 70°C. The conductivity of all samples increased with temperature and exhibited stable electrical behavior with increasing temperature. TGA analysis of samples showed that the composites were more stable than the homopolymers or PVF separately. The magnetic susceptibility values of samples were negative, except for PVF/PPy‐H₃BO₃. Morphology changes of the composites investigated by scanning electron microscopy (SEM), attributed to synthesis conditions, have a significant effect on their conductivity.     

Influence of HCL on polypyrrole films prepared chemically from ferric chloride

Smooth, adherent films of the electrically conducting polypyrrole formed on surfaces in contact with unstirred aqueous solutions containing the pyrrole monomer and the oxidant, FeCl₃. Contradictory reports in the literature concerning the influence of HCl on the growth rate and electrical conductivity of polypyrrole grown in this manner prompted this study of the growth rate and conductivity of films. With no intentional addition of HCl, the growth rate of the films, measured using a quartz crystal microbalance, was fit to a simple second-order model in which the rate was limited by the bulk depletion of reactants. The conductivity of the films was found to be about 1 S cm^?1. Both the growth rate and the electrical conductivity initially increased with the deliberate addition of HCl to the solution. The conductivity was found to peak at a value about 20 S cm^?1 at an initial HCl concentration of 0.3 M. At initial HCl concentration of 2M or more, films could not be grown. © 1994 John Wiley & Sons, Inc.     

Synthesis of electrically conductive polypyrrole-polystyrene composites using supercritical carbon dioxide: I. Effects of the blending conditions

The electrical conductivity for a polymer composite consisting of polypyrrole (PPy) and an insulating host polystyrene (PS) is reported in this study. The host polymer was blended with pyrrole monomer using either supercritical carbon dioxide (SCCO₂) or high-pressure liquid carbon dioxide (HPLCO₂) as the carrying solvent. After the blending process, the blended host polymer was soaked in an oxidant solution. This process is compared with that of oxidant impregnation. With the same processing conditions, a polymer composite with much higher conductivity was obtained when the blending process was carried out before doping in an oxidant agent. Scanning electron microscope (SEM) and elemental analysis reveal that polymerization proceeded when the blended host polymer was soaking in the oxidant solution. It is observed that SCCO₂ provides better conditions for blending the host polymer with pyrrole monomer than HPLCO₂ at the same density. The maximum conductivity of the polymer composites also increases with temperature and pressure at the same SCCO₂ density.     

纳米石墨薄片/聚吡咯复合材料的制备及导电性能

膨胀石墨经过超声处理制备了纳米石墨薄片。以其为导电填料，对甲苯磺酸为掺杂剂，FeCl₃·6H₂O为氧化剂，引发吡咯单体发生原位聚合，制备出纳米石墨薄片/聚吡咯(NanoGs/PPy)复合材料。利用红外光谱(FTIR)、扫描电镜(SEM)和透射电镜(TEM)表征了材料的组成和结构。结果表明，石墨薄片被聚吡咯完全包覆；并且以纳米级尺寸分散在聚吡咯基体中。热失重(TG)分析和电导率测试结果表明，复合材料的耐热性能和导电性能较纯聚吡咯有所提高。     

Unstirred preparation of soluble electroconductive polypyrrole nanoparticles

Soluble electro-conductive polypyrrole nanoparticles (PPY-NPs) doped with organic sulfonic acid can be easily prepared via a new method for unstirred polymerization. The yield, size, morphology, electrical conductivity and solubility of the PPY-NPs were optimized by changing the feeding oxidant method, the sulfonic acid, the oxidant, and steric stabilizers. The PPY-NPs were characterized by FTIR, wide angle X-ray diffraction and four-point probe techniques. The morphology of the nanoparticles was investigated using scanning electron microscopy (SEM) and transmission electron microscopy. The PPY-NPs doped with p-toluenesulfonic acid exhibit a small diameter, an electrical bulk conductivity of 52.7 S·cm^?1, and can be obtained in high yield. PPY-NPs doped with naphthalene-2-sulfonic acid have a minimum mean diameter of around 71 nm (as found by SEM). All doped PPY-NPs are well solube in dimethylformamide, dimethyl sulfoxide, formic acid and sulfuric acid.     

The Polymerization and Oxidation of Pyrrole by Halogens in Organic Solvents

Simultaneous chemical polymerization and oxidation of pyrrole have been initiated by a halogenic electron acceptor, bromine or iodine, in various organic solvents. The polypyrrole (PPY)-halogen charge transfer (CT) complexes obtained from polymerization in acetonitrile are of particular interest. Both the PPY-I₂ and PPY-Br₂ CT complexes are granular in nature and have an electrical conductivity in the order of 1 to 10 ohm^?1 cm^?1. Both complexes show remarkable stability in the atmosphere and in the presence of moisture. The PPY-I₂ and PPY-Br₂ CT complexes in the form of thin, coarse films have also been synthesized on a SnO₂ electrode by electrochemical polymerization in acetonitrile. The physicochemical properties of the PPY-I₂ and PPY-Br₂ CT complexes prepared by the chemical methods are characterized by means of UV-visible and IR absorption spectroscopy, thermal and chemical analysis, and electrical conductivity and density measurements.     

Electrically conductive composite prepared by template polymerization of pyrrole into a complexed polymer

Electrically conducting polymer composite films have been synthesized by the exposure of poly(4-vinylpyridine) complexed with cupric ions to pyrrole and water vapor. To immobilize a stoichiometric amount of the oxidant inside the polymer matrix, the ratio of poly(4-vinylpyridine)/cupric ion = 1.8 was chosen. Polypyrrole was formed in this tailored structure by a template polymerization process. Opaque polymer composite films with electrical conductivity up to 60 (Ω cm)^?1 have been obtained by this method, However, slightly colored transparent composite thin films with a conductivity as high as 50 (Ω cm)^?1 were also produced. The electrically conducting polymer composite films and the metal-polymer complex have been characterized by XPS and IR spectroscopy, elemental analysis, EDX, and scanning electron microscopy. The polymerization process was also followed by use of a quartz crystal microbalance. © 1994 John Wiley & Sons, Inc.     

Synthesis,core-shell structures and properties of fluorene/polypyrrole composite

In the current study, fluorene/polypyrrole composite with the core-shell structure has been synthesized by in situ oxidative polymerization of pyrrole in the presence of fluorene. Composite was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. Electrical performance of the composite prepared at various reaction conditions was tested. The composite has the best performance of electrical conductivity when FeCl₃–pyrrole molar ratio is equal to 3 and the reaction time is 18 h. It was found that polypyrrole could be formed on the surface of fluorene due to strong π–π interactions between the fluorene core and the polypyrrole shell.     

Preparation of Polypyrrole/Poly(methyl methacrylate) Core-Shell Nanoparticles in Four-Component Microemulsion Media

Electrically conductive polypyrrole (PPy)/poly(methyl methacrylate) (PMMA) core-shell nanoparticles were synthesized by two-step microemulsion polymerization. PPy core particles were prepared in a four-component microemulsion system, which was formed with surfactant cetyltrimethyl ammonium bromide (CTAB), cosurfactant n-pentanol, water, and pyrrole. Ferric chloride and iodine was added as the oxidant and the dopant, respectively. Then the PPy nanoparticles were coated with PMMA to prepare PPy/PMMA core-shell nanoparticles. The morphology of PPy/PMMA core-shell nanoparticles was characterized with transmission electron microscopy (TEM). Fourier transform infrared (FTIR) spectroscopy was used to characterize the structure of the samples. The electrical conductivities of samples were studied by a Hall effect testing instrument. Despite being coated with a layer of insulation, the conductivity of the composite PPy/PMMA core-shell nanoparticles could still reached to 7.856 × 10^?1 S/cm.     

Preparation and characterization of porous conducting poly(dl-lactide) composite membranes

Solid conducting biodegradable composite membranes have shown to enhance nerve regeneration. However, few efforts have been directed toward porous conducting biodegradable composite membranes for the same purpose. In this study, we have fabricated some porous conducting poly(dl-lactide) composite membranes which can be used for the biodegradable nerve conduits. The porous poly(dl-lactide) membranes were first prepared through a phase separation method, and then they were incorporated with polypyrrole to produce porous conducting composite membranes by polymerizing pyrrole monomer in gas phase using FeCl₃ as oxidant. The preparation conditions were optimized to obtain membranes with controlled pore size and porosity. The direct current conductivity of composite membrane was investigated using standard four-point technique. The effects of polymerization time and the concentration of oxidant on the conductivity of the composite membrane were examined. Under optimized polymerization conditions, some composite membranes showed a conductivity close to 10⁻³ S cm⁻¹ with a lower polypyrrole loading between 2 and 3 wt.%. A consecutive degradation in Ringer's solution at 37 °C indicated that the conductivity of composite membrane did not exhibit significant changes until 9 weeks although a noticeable weight loss of the composite membrane could be seen since the end of the second week.     

Systematic study on chemical oxidative and solid‐state polymerization of poly(3,4‐ethylenedithiathiophene)

Systematic research on the synthesis, chemical oxidative polymerization of 3,4‐ethylenedithiathiophene (EDTT) in the presence of surfactants or not, and solid‐state polymerization of 2,5‐dibromo‐3,4‐ethylenedithiathiophene (DBEDTT) and 2,5‐diiodo‐3,4‐ethylenedithiathiophene (DIEDTT) under solventless and oxidant‐free conditions has been investigated. Effects of oxidants (Fe³⁺ salts, persulfate salts, peroxides, and Ce⁴⁺ salts), solvents (H₂O, CH₃CN/H₂O, and CH₃CN), surfactants, and so forth on polymerization reactions and properties of poly(3,4‐ethylenedithiathiophene) (PEDTT) were discussed. Characterizations indicated that FeCl₃ was more suitable oxidant for oxidative polymerization of EDTT, while CH₃CN was a better solvent to form PEDTT powders with higher yields and electrical conductivities. Dispersing these powders in aqueous polystyrene sulfonic acid (PSSH) solution showed better stability and film‐forming property than sodium dodecylsulfate and sodium dodecyl benzene sulfonate. Oxidative polymerization of EDTT in aqueous PSSH solutions formed the solution processable PEDTT dispersions with good storing stability and film‐forming performance. Solvent treatment showed indistinctive effect on electrical conductivity of free‐standing PEDTT films. As‐formed PEDTT synthesized from solid‐state polymerization showed similar electrical conductivity, poorer stability, but better thermoelectric property than oxidative polymerization. Contrastingly, PEDTT synthesized from DIEDTT showed higher electrical conductivity (0.18 S cm^?1) than DBEDTT which showed better thermoelectric property with higher power factor value (6.7 × 10^?9 W m^?1 K^?2). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Fabrication of Electrically Conducting Polypyrrole‐Poly(ethylene oxide) Composite Nanofibers

Summary: Electrically conducting polypyrrole‐poly(ethylene oxide) (PPy‐PEO) composite nanofibers are fabricated via a two‐step process. First, FeCl₃‐containing PEO nanofibers are produced by electrospinning. Second, the PEO‐FeCl₃ electrospun fibers are exposed to pyrrole vapor for the synthesis of polypyrrole. The vapor phase polymerization occurs through the diffusion of pyrrole monomer into the nanofibers. The collected non‐woven fiber mat is composed of 96 ± 30 nm diameter PPy‐PEO nanofibers. FT‐IR, XPS, and conductivity measurements confirm polypyrrole synthesis in the nanofiber.

An SEM image of the PPy‐PEO composite nanofibers. The scale bar in the image is 500 nm.     

The development of conductive composite surfaces by a diffusion-limited in situ polymerization of pyrrole in sulfonated polystyrene ionomers

Electrically conductive composite surfaces were prepared by a diffusion-controlled in situ polymerization of pyrrole in the surface layer of sulfonated polystyrene ionomer films. Premolded films of the ionomer sulfonic acid derivatives were sequentially immersed in aqueous solutions of pyrrole and FeCl₃, and polymerization occurred only where both the monomer and the oxidant were present. The penetration of the polypyrrole (PPy) into the film was controlled by varying the immersion time in the monomer solution. The amount of PPy produced depended on the immersion time of the film in the monomer and the degree of sulfonation of the ionomer. Surface conductivities of 10⁻⁴-10⁻¹ S/cm were achieved with PPy concentrations from 2 to 22 wt % and composite layers as thin as 15 μm. Intermolecular interactions occurred between PPy and the ionomer by proton transfer. Incorporation of PPy also increased the tensile strength of the ionomer film, significantly increased its modulus above T_g, and inhibited melt flow. © 1997 John Wiley & Sons, Inc.     

Synthesis of polypyrrole micro/nanofibers via a self-assembly process

Novel polypyrrole (PPy) micro/nanofibers were synthesized via a self-assembly process by using 4-hydroxy-3-[(4-sulfo-1-naphthalenyl) azo]-1-naphthalenesulfonic acid (Acid Red B) as dopant and ferric chloride (FeCl₃) as oxidant. Experimental conditions, including the concentration of the dopant, reaction temperature and stirring state have been investigated for their influences on the morphology of the synthesized PPy micro/nanofibers. The products were characterized by scanning electron microscopy, transmission electron microscopy and Fourier-transform infrared spectroscopy. The formation mechanism of micro/nanofibers was studied. It is believed that the micelles formed by the dopant and pyrrole monomer act as templates during the synthesis process. Two functions of aggregation and synthesis are proposed in the reaction system simultaneously, and the morphologies of micro/nanofibers are the co-operations of these two functions. The maximum conductivity value of the PPy micro/nanofibers was 8.56 S cm^?1     

A study of polypyrrole synthesized with oxidative transition metal ions

Polypyrrole powder and films were chemically synthesized by the reaction of AgNO₃, FeCl₃, Fe(NO₃)₃, Cu(NO₃)₂, or Cu(NO₃)₂-AlCl₃ with pyrrole in an aqueous solution or a water—toluene two-phase system. Products were characterized by elemental analysis, IR, scanning electron microscopy with energy dispersive x-ray analysis (SEM with EDAX), and conductivity measurements. The polypyrrole synthesized from pyrrole with FeCl₃ had a composition of C_4.00H_3.05N_0.99Cl_0.25. The pressed powder had a conductivity of 2.7 × 10^?2 S/cm and the film 2.8 S/cm. All the other metal salts produced films that had the same organic backbone, morphology, and conductivity as the polymer synthesized using Fe(III) salts, regardless of the considerable differences in the reduction potentials of the metal ions. The nature of the anions of the transition metal salts had no effect on the reaction. Anions, however, were retained as the counterions of the cationic polypyrrole backbone and could be easily exchanged with other anions.     

Chemical and electrochemical characterization of chemically synthesized conducting polypyrrole

The conducting polypyrrole chemically synthesized in water, using the variable concentrations of FeCl₃ and CuCl₂ as oxidizing agents, was chemically and electrochemically characterized and compared with electrochemically generated polypyrrole. According to the results of elemental analysis and counter ion determinations, it can be concluded that a mixture of dimer and trimer was obtained using CuCl₂, i.e., a dimer composition using FeCl₃ as an oxidant. Cyclic voltammetric studies of polypyrrole obtained by using FeCl₃ as an oxidant showed no evidence of polypyrrole decomposition after repetitive cycling. The voltammograms showed also that after the oxidation reaction a high capacitive current remained, confirming the assumption that the capacitive current is intrinsically associated with polypyrrole, irrespective of the way of its preparation. Cyclic voltammogram of the polypyrrole synthesized by oxidation with CuCl₂ showed different shape, probably influenced by the presence of copper ions incorporated in polymers. © 1992 John Wiley & Sons, Inc.     

Electrochemical Interrogation and Sensor Applications of Nanostructured Polypyrroles

The polymerization of pyrrole in β‐naphthalene sulfonic acid (NSA) gave nanotubules, nanomicelles or nanosheets of polypyrrole (PPy) depending on the amount of NSA in the polymer and the temperature of the reaction. Scanning electron microscopy (SEM) measurements showed that the diameters of the nanostructured polypyrrole‐β‐naphthalene sulfonic acid (PPyNSA) composites were 150–3000 nm for the tubules, 100–150 nm for the micelles and 20 nm for the sheets. A red shift in the UV‐vis absorption spectra of PPy was observed for PPyNSA which indicates the involvement of bulky β‐naphthalene sulfonate ion in the polymerization process. The UV‐vis also showed the existence of polaron and bi‐polaron in the polymer which may be responsible for the improved solubility of PPyNSA compared to PPy. All the characteristic IR bands of polypyrrole were observed in the FTIR spectra of PPyNSA, with slight variation in the absolute values. However, the absence of N? H stretching at 3400 cm^?1 and 1450 cm^?1 usually associated with neutral polypyrrole confirms that the polymer is not in the aromatic state but in the excited polaron and bipolaron defect state. Electrochemical analysis of PPyNSA reveals two redox couples: a/a′ – partly oxidized polypyrrole‐naphthalene sulfonate radical cation/neutral polypyrrole naphthalene sulfonate; b/b′ – fully oxidized naphthalene sulfonate radical cation/partly reduced polypyrrole‐naphthalene sulfonate radical anion. The corresponding formal potentials measured at 5 mV/s, E°′_{(5 mV/s)}, are 181 mV and 291 mV, respectively. Amperometric phenol sensor constructed with PPyNSA on a glassy carbon electrode (GCE) gave a sensitivity of 3.1 mA M^?1 and a dynamic linear range of 0.65–139.5 μM. The data for the determination of phenol on the GCE/PPyNSA electrode was consistent with the electrocatalytic Michaelis‐Menten model, giving an apparent Michaelis‐Menten constant (K_M′) value of 160 μM.     

Polymerization and oxidation of pyrrole by organic electron acceptors

Simultaneous chemical polymerization and oxidation of pyrrole have been initiated by organic electron acceptors, 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetrachloro-o-benzoquinone(chloranil). The polypyrrole (PPY) complexes so produced are semiconductive and granular in nature. For the PPY–DDQ and PPY–chloranil complexes obtained from bulk polymerization, the respective electrical conductivities (σ) are of the order of 10^?1 and 10^?3 ohm^?1 cm^?1. However, σ is substantially lower for the complexes prepared in solvent media. Both complexes are relatively stable in the atmosphere. Thin uniform films of the PPY–organic acceptor complexes have also been synthesized on SnO₂ electrode by electrochemical polymerization in acetonitrile. The physicochemical properties of the PPY–organic acceptor complexes prepared chemically under the various experimental conditions are examined in detail.     

The calorimetric determination of the ceiling temperature for the chemical polymerization of pyrrole

The previously found strong dependence of the polymerization enthalpy on the reaction temperature has been rationalized. The temperature dependence is to be ascribed to the existence of a ‘ceiling temperature’ for the polymerization process of the pyrrole monomer. The determined ceiling temperature has beenT?350 K when FeCl₃ was used as the oxidizing agent in CH₃CN solution. The existence of a ceiling temperature together with its already determined exoenthalpic nature allows to classify the polymerization reaction as an exoentropic one. From the dependence of the yield of insoluble polymer on the reaction temperature, the trend of the relative mean numeral molecular massM _n for the different obtained polymers has been determined. Measurements of electrical conductivity on pressed pellets of the different polymers allowed to establish a correlation between theM _n value and the conductivities The dependence of the conductivity on the exposition time to the air allowed to do some essays on the aging behaviour of the obtained polypyrrole. By making some assumptions, an absolute calorimetric determination of the value ofM _n of polypyrrole was tempted together with that of the related poly-N-vinilpyrrole.