Conducting polymers chemical synthesis

Sherman, B. C., W. B. Euler, and R. R. Force. 1994. Polyaniline—A conducting polymer electrochemical synthesis and electrochromic properties. Journal of Chemical Education 71 (4) A94-A95. 

Although most metal-containing polythiophenes have been synthesized by electropolymerization on an electrode surface, there are many reasons to chemically synthesize these polymers. Chemical synthesis may allow isolation of soluble polymers, enabling complete solution characterization (GPC, light scattering, NMR, etc.) and facilitating conductivity studies. Moreover, it can enable improved thin-film preparation and film deposition onto nonconducting substrates. Finally, monomers that are unsuitable for electropolymerization may be polymerized by chemical methods. 

Section 2 mainly focuses on generic synthesis of conducting polymers chemical oxidation and electrochemical polymerization. Although a large amount of work has been devoted to characterize physical and chemical properties of newly developed conducting polymers, this part only describes the information of synthetic methodology of conducting polymers. 

Empirical kinetics are useful if they allow us to develop chemical models of interfacial reactions from which we can design experimental conditions of synthesis to obtain thick films of conducting polymers having properties tailored for specific applications. Even when those properties are electrochemical, the coated electrode has to be extracted from the solution of synthesis, rinsed, and then immersed in a new solution in which the electrochemical properties are studied. So only the polymer attached to the electrode after it is rinsed is useful for applications. Only this polymer has to be considered as the final product of the electrochemical reaction of synthesis from the point of view of polymeric applications. 

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. 

Chemical and electrochemical techniques have been applied for the dimensionally controlled fabrication of a wide variety of materials, such as metals, semiconductors, and conductive polymers, within glass, oxide, and polymer matrices (e.g., [135-137]). Topologically complex structures like zeolites have been used also as 3D matrices [138, 139]. Quantum dots/wires of metals and semiconductors can be grown electrochemically in matrices bound on an electrode surface or being modified electrodes themselves. In these processes, the chemical stability of the template in the working environment, its electronic properties, the uniformity and minimal diameter of the pores, and the pore density are critical factors. Typical templates used in electrochemical synthesis are as follows ... 

The synthesis of conducting polymers can be divided into two broad areas, these being electrochemical and chemical (i.e., non-electrochemical). Whilst the latter may be considered to be outside the scope of this review, it is worth noting that many materials which are now routinely synthesised electrochemically were originally produced via non-electrochemical routes, and that whilst some may be synthesised by a variety of methods many, most notably polyacetylene, are still only accessible via chemical synthesis. In view of this it is useful to have an appreciation of the synthesis of these materials via routes which do not involve electrochemistry. 

Title Chemical Synthesis of Chiral Conducting Polymers... 

Much work has been directed towards the synthesis of thiophene oligomers and polymers. This is due to the current interest in research on conducting polymers and molecular electronics (92CRV711). Two main approaches have been used for making such polymers (i) chemical (e.g. FeCl3) or electrochemical oxidation of monomeric thiophenes and (ii) transition metal-catalyzed cross-coupling reactions. 

PolyQj-Phenylene) is probably the most thermally and oxidatively stable conducting polymer known and has been of interest to polymer scientists both for its conducting properties and for its stability. Its synthesis by step-reaction polymerization or by chemical or electrochemical oxidation invariably gives powders or rather poor quality films, so that a precursor route would be very attractive. 

It should be mentioned that the defined interaction of dextran sulfate with amino functions is not only applied for the design of structures on the su-permolecular level but also on the molecular level. Thus, a preferred handed helical structure was induced into the polyaniline main chains by chemical polymerisation of achiral aniline in the presence of dextran sulfate as a molecular template. This affords a novel chemical route for the synthesis of chiral conducting polymers [158]. 

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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