Electropolymerization polythiophenes

Next, in the 1980s, the organic multilayer structures, which are another key technology of present high-performance OLEDs, appeared. In 1986, Hayashi et al. observed a remarkable reduction of the driving voltage by inserting a polythiophene-electropolymerized thin film between an indium-tin-oxide (ITO) anode and a perylene-deposited film.30 The insertion of the polythiophene thin... 

Other workers have studied polythiophene electropolymerization with two-parameter ellipsometry. The importance of experimental conditions in the... 

Besides synthesis, current basic research on conducting polymers is concentrated on structural analysis. Structural parameters — e.g. regularity and homogeneity of chain structures, but also chain length — play an important role in our understanding of the properties of such materials. Research on electropolymerized polymers has concentrated on polypyrrole and polythiophene in particular and, more recently, on polyaniline as well, while of the chemically produced materials polyacetylene stih attracts greatest interest. Spectroscopic methods have proved particularly suitable for characterizing structural properties These comprise surface techniques such as XPS, AES or ATR, on the one hand, and the usual methods of structural analysis, such as NMR, ESR and X-ray diffraction techniques, on the other hand. 

Some progress has also been achieved in the use of chiral polymer films at electrodes. Conductive polythiophenes containing optically active substituents in the 3-positions were prepared by electropolymerization of suitable monomers without apparent lc s of optical activity The polymer of exhibits distinct... 

Composites can also be prepared by electropolymerization from solutions containing dissolved polymer 307). Since films of polypyrrole or polythiophene are normally porous, it seems most likely that the dissolved polymer is simply entrained in the pores. Similarly, composites have been prepared by polymerization of pyrrole in the presence of acrylic latex, giving blends with 10-30 % polypyrrole that are conducting yet processable 808). Presumably the polypyrrole is distributed throughout the latex particles. 

As already pointed out above, electropolymerization has many variables which are difficult to control, and thus the structural parameters of the materials obtained tend to be variable. For example, depending on the electrochemical procedures used for the preparation of polythiophene, the conductivity can vary from 0.1 to 1000 S cm-1. This may be due to chain defects, the orientation of chains and the molecular weight the shorter the chain length, then the lower the conductivity is expected to be, since the conjugation is broken. 

It has been mentioned already that polypyrrole (25) and polythiophene (26) play an important role as electrical conductors and polymeric anodes in battery cells [2,47,226]. Since the charging and discharging of the conjugated polymer is accompanied by the incorporation and removal of counterions it is clear that the material can also act as a carrier of chemically different anions which influence the physical, chemical and physiological properties of the material [292]. With regard to the full structural elucidation of the polymers it must be added, however, that the electropolymerization process of pyrrole and thiophene does not provide a clean coupling of the heterocycles in the 2,5-positions. Instead, the 3- and 4-position can also be involved giving rise to further fusion processes under formation of complex polycyclic structures [47]. 

The formation of conductive conjugated polymers [e.g., polyacetylene, polypyrrole, polythiophene, polyaniline and poly(p-phenylene)] [92, 94] on electrodes by electropolymerization has been studied thoroughly [95]. If the electropolymerization is performed in a solution containing both the monomer and enzyme, then enzymes present in the immediate vicinity of the electrode surface become trapped in the... 

Thienyl)ethanol as a starting material will give monomers with an ether linkage in the substituent at the 3-position. Such monomers, once polymerized, have exhibited the ability to complex cations such as Li in a loose crown ether type structure [70]. This in turn leads to enhanced conductivity of the polymer when such cations are part of the supporting electrolyte. An added benefit of electropolymerization of polythiophene originates from the fact that sulfur has a tendency to physisorb to metals such as gold and platinum, which are electrode materials. Hence they may enhance the adsorption of polymer to the electrode and thus improve the physical stability of the system, as well as the extent of polymer/electrode interaction. The synthesis of these type of monomers (e.g., 60) is shown in Scheme 10-28. 

Composites of polypyrrole and poly(vinyl chloride) have been prepared by several groups (64-67). Polythiophene-poly(vinyl chloride) composites have also been prepared (68). The electropolymerization of pyrrole on poly(vinyl chloride)-coated electrodes yielded composites with mechanical properties (tensile strength, percent elongation at break, percent elongation at yield) similar to poly(vinyl chloride) (65) but with a conductivity of 5-50 S/cm, which is only slightly inferior to polypyrrole (30-60 S/cm) prepared under similar conditions. In addition, the environmental stability was enhanced. Morphological studies (69) showed that the polypyrrole was not uniformly distributed in the film and had polypyrrole-rich layers next to the electrode. Similarly, poly(vinyl alcohol) (70) poly[(vinylidine chloride)-co-(trifluoroethylene)] (69) and brominated poly(vinyl carbazole) (71) have been used as the matrix polymers. The chemical polymerization of pyrrole in a poly(vinyl alcohol) matrix by ferric chloride and potassium ferricyanide also yielded conducting composites with conductivities of 10 S/cm (72-74). 

Oxide, flouride, and polymeric films, as well as certain others, are used as protective coatings for HTSC materials (for example, see [505]). The electrodeposition of conducting polymers such as polypyrrole [433,491, 493, 506], polythiophene and its derivatives [493, 507], and polyaniline [478] is the most effective process. Anodic electropolymerization in acetonitrile solutions proceeds without any degradation of the HTSC substrate and ensures continuous and uniform coatings. Apparently, this method is promising not only for the fabrication of compositions with special properties based on HTSC [50, 28,295] as mentioned above, but also for the creation of junctions with special characteristics [507]. 

Scheme 1. (Left) Synthesis of Polyaniline by Electropolymerization in the Presence of an Optically Active Acid and (Right) Structure of Oxazoline-Containing Polythiophene 29...

As with polypyrroles, the counterion used during electropolymerization influences the conductivity of polythiophenes.120121 Electrochemically produced copolymers122 of 3-dodecylthiophene (DTh) and 3-methylthiophene (MTh) have been shown to exhibit conductivities intermediate to the two homopolymers. The actual value depends on the ratio of MTh to DTh in the polymer. 

As with polyanilines, polythiophenes can either be prepared directly by electropolymerization, or by casting from solutions (for alkyl-substituted thiophenes). Most interest has focused on the latter because of their improved mechanical properties compared with those of electrochemically prepared films. The factors influencing the mechanical properties of PTh s are reviewed in this section. 

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