Poly conducting polymer solution

Membrane keypads face significant competition from new technologies now being developed. For example, research at the University of Pennsylvania and Yamanashi University, by Hohnholz, Okuzaki and MacDiarmid [5], involves the fabrication of a polymer-dispersed fiquid crystal display using electrodes of poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) in conjunction with a push-button keyboard array. The display is produced by the design and printing of a line pattern on a substrate which is then coated with a conductive polymer solution. Subsequently the reverse-printed toner pattern is removed. 

The huge literature on the electronic conductivity of dry conducting polymer samples will not be considered here because it has limited relevance to their electrochemistry. On the other hand, in situ methods, in which the polymer is immersed in an electrolyte solution under potential control, provide valuable insights into electron transport during electrochemical processes. It should be noted that in situ and dry conductivities of conducting polymers are not directly comparable, since concentration polarization can reduce the conductivity of electrolyte-wetted films considerably.139 Thus in situ conductivities reported for polypyrrole,140,141 poly thiophene,37 and poly aniline37 are orders of magnitude lower than dry conductivities.15... 

On the other hand, Doblhofer218 has pointed out that since conducting polymer films are solvated and contain mobile ions, the potential drop occurs primarily at the metal/polymer interface. As with a redox polymer, electrons move across the film because of concentration gradients of oxidized and reduced sites, and redox processes involving solution species occur as bimolecular reactions with polymer redox sites at the polymer/solution interface. This model was found to be consistent with data for the reduction and oxidation of a variety of species at poly(7V-methylpyrrole). This polymer has a relatively low maximum conductivity (10-6 - 10 5 S cm"1) and was only partially oxidized in the mediation experiments, which may explain why it behaved more like a redox polymer than a typical conducting polymer. 

Initially alkynes were polymerised by trial and error with the use of Ziegler type recipes and the mechanism for these reactions may well be an insertion type mechanism. Undefined metathesis catalysts of ETM complexes were known to give poly-acetylene in their reaction with alkynes (acetylene) [45] and metallacycles were proposed as intermediates. Since the introduction of well-defined catalysts far better results have been obtained. The mechanism for this reaction is shown in Figure 16.24 [46], The conductive polymers obtained are soluble materials that can be treated and deposited as solutions on a surface. 

Ionic charges of the polymers were determined by photometric colloid titrations in some instances. A known amount of poly(diallyldimethylammonium chloride) was added to the polymer solution at a pH of 2.5. The excess poly(diallyldimethylammonium chloride) was titrated by poly(vinylsulfate) using the adsorption indicator methylene blue. The end point was detected by the photometric detector as the color of the solution changes from blue to violet. For anionic copolymers the colloid titration was conducted at pH values of 2.5 and 10.0 to determine the extent of modification. 

Against this background of infusible conducting polymers, the development of the soluble polythiophenes is most interesting. Glass transition temperatures have been reported as 48 °C for poly(3-butylthiophene) and 145 °C for poly(3-methyl-thiophene) 261). These polymers also show crystallinity in films and can be crystallized from solution. Solution studies indicate that there are two chain conformations 262) and the availability of a non-conjugated conformation may be a key to the low transition temperatures and solubility, when compared to the stiff-chain conjugated polymers. 

The soluble polythiophenes are the first conducting polymers that can be taken above their glass transition without decomposition and it will be interesting to study morphology-property relationships. Heeger et al.262) have recently described conformational changes in solutions of poly-3-hexylthiophene which seem to involve a coil-helix transformation as the temperature is decreased or a poor solvent is added. 

Solid-state ISEs with conducting polymers are also promising for low-concentration measurements [60,63,74], even below nanomolar concentrations [60,74], which gives rise to optimism concerning future applications of such electrodes. In principle, the detection limit can be improved by reducing the flux of primary ions from the ion-selective membrane (or conducting polymer) to the sample solution, e.g., via com-plexation of primary ions in the solid-contact material. For example, a solid-state Pb2+-ISEs with poly(3-octylthiophene) as ion-to-electron transducer coated with an ion-selective membrane based on poly(methyl methacrylate)/poly(decyl methacrylate) was found to show detection limits in the subnanomolar range and a faster response at low concentrations than the liquid-contact ISE [74]. 

Figure 3.16 Ionic electrical conductivity for solutions of lithium triflate in solid poly[fc (methoxyethoxyethoxy)phosphazene] ( MEEP ) is believed to occur following coordination of the etheric side groups to Li+ ions, cation-anion separation, ion transfer from one polymer to another as the polymer and side groups undergo extensive thermal motions. From Shriver and Farrington, Chem. Eng. News, 1985, 42-57 (May 20). Reprinted by permission of the American Chemical Society.

As was mentioned above, conjugated organic polymers in their pristine state, are electrical insulators or, at best, semi-conductors. Their conductivity can be increased by orders of magnitude by a doping process. In the "doped" state, the backbone of a conducting polymer consists of a delocalised 7i-system. Early in the twenty-first century Schon et al. (2001) discovered super-conduction in solution cast doped regioregular poly(3-hexylthio-phene) at temperatures below 2.35 K The appearance of superconductivity seems to be... 

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