Conducting polymers preparation methods

Table 1. Conducting polymers preparation methods and conductivities...

Shen et al. [75] measured the electrical conductivity of polyethylene/maleic anhydride-grafted polyethylene/graphite nanocomposites. Electrical conductivity and morphology were influenced by the polymer preparation method and could be explained in terms of percolation theory. 

Polymers. The Tt-conjugated polymers used in semiconducting appHcations are usually insulating, with semiconducting or metallic properties induced by doping (see Flectrically conductive polymers). Most of the polymers of this type can be prepared by standard methods. The increasing use of polymers in devices in the last decade has led to a great deal of study to improve the processabiUty of thin films of commonly used polymers. 

Electrochemical polymeriza tion of heterocycles is useful in the preparation of conducting composite materials. One technique employed involves the electro-polymerization of pyrrole into a swollen polymer previously deposited on the electrode surface (148—153). This method allows variation of the physical properties of the material by control of the amount of conducting polymer incorporated into the matrix film. If the matrix polymer is an ionomer such as Nation (154—158) it contributes the dopant ion for the oxidized conducting polymer and acts as an effective medium for ion transport during electrochemical switching of the material. 

Many other opportunities exist due to the enormous flexibility of the preparative method, and the ability to incorporate many different species. Very recently, a great deal of work has been published concerning methods of producing these materials with specific physical forms, such as spheres, discs and fibres. Such possibilities will pave the way to new application areas such as molecular wires, where the silica fibre acts as an insulator, and the inside of the pore is filled with a metal or indeed a conducting polymer, such that nanoscale wires and electronic devices can be fabricated. Initial work on the production of highly porous electrodes has already been successfully carried out, and the extension to uni-directional bundles of wires will no doubt soon follow. 

In the early work on the thermolysis of metal complexes for the synthesis of metal nanoparticles, the precursor carbonyl complex of transition metals, e.g., Co2(CO)8, in organic solvent functions as a metal source of nanoparticles and thermally decomposes in the presence of various polymers to afford polymer-protected metal nanoparticles under relatively mild conditions [1-3]. Particle sizes depend on the kind of polymers, ranging from 5 to >100 nm. The particle size distribution sometimes became wide. Other cobalt, iron [4], nickel [5], rhodium, iridium, rutheniuim, osmium, palladium, and platinum nanoparticles stabilized by polymers have been prepared by similar thermolysis procedures. Besides carbonyl complexes, palladium acetate, palladium acetylacetonate, and platinum acetylac-etonate were also used as a precursor complex in organic solvents like methyl-wo-butylketone [6-9]. These results proposed facile preparative method of metal nanoparticles. However, it may be considered that the size-regulated preparation of metal nanoparticles by thermolysis procedure should be conducted under the limited condition. 

Electrochemistry is one of the most promising areas in the research of conducting polymers. Thus, the method of choice for preparing conducting polymers, with the exception of PA, is the anodic oxidation of suitable monomeric species such as pyrrole [3], thiophene [4], or aniline [5]. Several aspects of electrosynthesis are of relevance for electrochemists. First, there is the deposition process of the polymers at the electrode surface, which involves nucleation-and-growth steps [6]. Second, to analyze these phenomena correctly, one has to know the mechanism of electropolymerization [7, 8]. And thirdly, there is the problem of the optimization of the mechanical, electrical, and optical material properties produced by the special parameters of electropolymerization. 

Brown et al. 3S2) have recently emphasised the role of defect structures in heterocyclic polymers. They point out that the reported doped conductivities of these polymers may vary by as much as six orders of magnitude depending on the preparation procedure. They have applied the laser desorption method, discussed earlier for polyphenylene, to a range of polyheterocycles. Unlike polyphenylene, there was evidence for incomplete desorption and rearrangement of evaporated molecules. The results show that polymers prepared by Grignard coupling vary in their extent of bromination, the nature of the terminal species and the extent of formation of cyclic, polynuclear contaminants. 

In recent years the electrochemistry of the enzyme membrane has been a subject of great interest due to its significance in both theories and practical applications to biosensors (i-5). Since the enzyme electrode was first proposed and prepared by Clark et al. (6) and Updike et al. (7), enzyme-based biosensors have become a widely interested research field. Research efforts have been directed toward improved designs of the electrode and the necessary membrane materials required for the proper operation of sensors. Different methods have been developed for immobilizing the enzyme on the electrode surface, such as covalent and adsorptive couplings (8-12) of the enzymes to the electrode surface, entrapment of the enzymes in the carbon paste mixture (13 etc. The entrapment of the enzyme into a conducting polymer has become an attractive method (14-22) because of the conducting nature of the polymer matrix and of the easy preparation procedure of the enzyme electrode. The entrapment of enzymes in the polypyrrole film provides a simple way of enzyme immobilization for the construction of a biosensor. It is known that the PPy-... 

Chemical preparation methods for the synthesis of conducting polymers have been widely used [35]. It has become clear that to fully exploit the potential of the conducting polymer, better-defined soluble materials with a clear correlation between structure and properties need to be prepared. In this section, monosubstituted alkylthiophenes will be discussed as an example of how, via the development of well-documented systematic methods, ordered polymer layers can be obtained with improved conductive properties. 

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