conductive polymers

8
REVIEW ARTICLE ADVANCES IN CONDUCTIVE POLYMERS D. KUMAR* and R. C. SHARMA Department of Applied Chemistry, Delhi College of Engineering, University of Delhi, Delhi-110006, India (Received 12 August 1996; accepted in ®nal form 30 April 1997) AbstractÐConductive polymers are a new class of materials which exhibit highly reversible redox beha- viour and the unusual combination of properties of metal and plastics. The prospective utility of con- ductive polymers with a potent application in number of growing technologies in biomolecular electronics, telecommunication, display devices and electrochemical storage systems, etc. has further enhanced the interest of researchers in this novel area. An eort has been made in this article to present an updated review on the various aspects of conductive polymers, viz. synthesis of conductive polymers, doping, structure analysis and proposed utility for further study of the future scienti®c and technologi- cal developments in the ®eld of conductive polymers. # 1998 Elsevier Science Ltd. All rights reserved INTRODUCTION The discovery of conductive polymers is unique in its accomplishment as a possible substitute for met- allic conductors and semiconductors. The eorts for having a tailor-made polymer in respect of its elec- trical, mechanical, optical and thermal properties have been pursued by several research groups. It was thus felt that a comprehensive review devoted entirely to the current understanding and state-of- the-art, derived from the existing published exper- imental and theoretical data of conductive polymers including those based on aromatic systems, would be highly desirable and inspire the dedicated researchers' venture into new experiments. The development of polymers with conductivities equal to semiconductors and metals have been presented in Table 1 and their corresponding structures are shown in Fig. 1. The conductive polymers belonging to polyenes or polyaromatics such as polyacetylene, polyaniline, polypyrrole, polythiophene, poly( p-phenylene), poly(phenylene vinylene) classes have been studied extensively. Among all the above classes, the polya- niline family of conjugated polymers is of much interest worldwide because of its unique conduction mechanism and good environmental stability in the presence of oxygen and water. Polyaniline is one of the oldest conductive polymers known. It was ®rst prepared by Letheby in 1862 by anodic oxidation of aniline in sulphuric acid and described as existing in four dierent states, each of which was an octa- mer. The decade of the 1970 s witnessed the evol- ution of a variety of conductive polymers [1±4], but poor solubility in most of the common solvents and low thermoplasticity rendered the processing of conductive polymers research to prepare soluble forms of conductive polymers. A summary of the reported literature highlighting the polymerisation techniques of conductive polymers is presented in Table 2 [5±26]. Bryce et al. [7] prepared the soluble form of polythiophene by substitution in the thio- phene ring's 3 position of either a methoxy group or long-chain alkyl groups and Macinnes and Funt [8] prepared the polyaniline by substitution in the ortho position of benzene ring in aniline. To study the thermal behaviour, Mcghie [27] reviewed the thermal analysis of polymers, with discussion par- ticularly on TGA, DSC and thermochemical analy- sis, while Gedde [28] reviewed DSC, DTA, thermogravimetry, thermal mechanical analysis and thermal optical analysis and presented the interpret- ation of the consequences. The development of the ®eld of conductive polymers has been comprehen- sively reviewed, as in an earlier report in compi- lation volumes edited by Lund and Baizer [29], Gerischer and Tobias [30], Margolis [31], Linford [32] and by Chandler and Pletcher [33]. Other reviews include those by Deronzier and Moutet [34], Heinze [35], Simonet and Rault-Berthelot [36] and Imisides et al. [37]. This review has been struc- tured to present an overview on preparations, dop- ing, proposed utilities and concluding remarks on conjugated polymers. SYNTHESIS There is no singular method for synthesising polymers that can be transformed into conductive polymers, the incorporation of extended p-electron conjugation is of foremost importance. Conductive polymers except ionomeric polymers may be syn- thesised using standard methods of polymerisation [38±41] including conventional as well as speci®c routes which include Witting, Horner and Grignard reactions, polycondensation processes and metal Eur. Polym. J. Vol. 34, No. 8, pp. 1053±1060, 1998 # 1998 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0014-3057/98 $Ðsee front matter PII: S0014-3057(97)00204-8 *To whom all correspondence should be addressed. 1053

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