Polypyrroles, properties electrical

The discovery that doped forms of polypyrroles conduct electrical current has spurred a great deal of synthetic activity related to polypyrroles [216-218], Reviews are available on various aspects of the synthesis and properties of polypyrroles [219,220]. In addition, summaries of important aspects of polypyrroles are included in several reviews on electrically conducting polymers [221-226]. Polypyrrole has been synthesized by chemical polymerization in solution [227-231], chemical vapor deposition (CVD) [232,233], and electrochemical polymerization [234-240]. The polymer structure consists primarily of units derived from the coupling of the pyrrole monomer at the 2,5-positions [Eq. (84)]. However, up to a third of the pyrrole rings in electrochemically prepared polypyrrole are not coupled in this manner [241]. 

The nature and concentration of the dopant are important factors in controlling the physiochemical and mechanical properties of the polymer and its conductivity and long-term stability (54). Several dopants have been proposed, including bromine, iodine, lithium perchlorate, ferric chloride, cupric chloride, hydrogen peroxide, lead dioxide, nitrous acid, quinones, ozone (55), as well as 2-naphthalenesulfonate and p-toluenesulfonate (56). Some of these have been studied by Myers (47), who found that ferric chloride under anhydrous conditions yields the most conductive polypyrrole, with electrical conductivity as high as 45 S/cm. Park and Ruckenstein (21) also reported that ferric chloride provides the best performance as an oxidant. 

There are several reports of Ag nanocomposites with conducting polymers like polyaniline [38] and polypyrrole [39]. However, electrical conducting properties of green metal - starch... 

X. Zhang, J. Zhang, R. Wang, T. Zhu, and Z. Liu, Surfactant-directed polypyrrole/CNT nanocables synthesis, characterization, and enhanced electrical properties. ChemPhysChem 5, 998—1002 (2004). 

An extensive review of the synthesis of rc-conjugated polymers is presented using a tutorial approach to provide an introduction to the field intended for the undergraduate student and the experienced chemist alike. The many synthetic methodologies that have been used for the synthesis of conjugated polymers are outlined for each class of polymers with a focus on research from the 1990s. The effect of structure on electrical properties is detailed. Specific systems reviewed include the polyacetylenes, polyanilines, polypyrroles, polythiophenes, poly(arylene vinylenes), and polyphenylenes. 

Comparable to thiophene, pyrrole is a five-membered heterocycle, yet the ring nitrogen results in a molecule with distinctly different behavior and a far greater tendency to polymerize oxidatively. The first report of the synthesis of polypyrrole (PPy) 62 that alluded to its electrically conductive nature was published in 1968 [263]. This early material was obtained via electrochemical polymerization and was carried out in 0.1 N sulfuric acid to produce a black film. Since then, a number of improvements, which have resulted from in-depth solvent and electrolyte studies, have made the electrochemical synthesis of PPy the most widely employed method [264-266]. The properties of electrosynthesized PPy are quite sensitive to the electrochemical environment in which it is obtained. The use of various electrolytes yield materials with pronounced differences in conductivity, film morphology, and overall performance [267-270]. Furthermore, the water solubility of pyrrole allows aqueous electrochemistry [271], which is of prime importance for biological applications [272]. 

CP sensors [17] exploit the electrochemical properties of compounds such as polypyrrole and polyindole. Films of the polymers are deposited on electrical conductor components. When analyte molecules are absorbed into the film the conductivity changes. The activity of CP films is fine-tuned by derivatizing the polymer with different functional groups thereby rendering the CP sensors... 

Two nitrogen-containing electroactive polymers, polypyrrole (PPY) [21] and polyaniline (PAN) [22], have been of particular interest because of their environmental stability, high electrical conductivity and interesting redox properties associated with the chain heteroatoms. More importantly, PAN has been found to exhibit solution processability [23, 24] and partial crystallinity [25,26]. 

Polypyrrole composite biomaterials having electrically conductive properties have been prepared using hyaluronic acid or its sodium salt by galvanostatic and potentio-static methods. These agents are useful for preparing medical devices such as nerve and bone regeneration materials. 

Lee [6] observed that when polyaniline or polypyrrole were N-functionalized with Wt-butoxy carbonyl, these materials displayed enhanced physical and mechanical properties with higher solubility and electrical conductivity than the corresponding nonfimctionalized counterparts. 

Toward an understanding of the conduction properties of polythiophenes (26) and polypyrroles (25) a large number of soluble oligomers has been prepared. Oligothiophenes, indeed, represent the most common model compounds for electrically conducting polymers [149]. Thereby, lower oligomers... 

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]. 

As mentioned in the introduction, the electrical conductivity upon doping is one of the most important physical properties of conjugated polymers. The conductivity ranges from lOOOOOS/cm for iodine-doped polyacetylene [41], 1000 S/cm for doped and stretched polypyrrole [42], to 500 S/cm for doped PPP [43], 150 S/cm for hydrochloric acid doped and stretched polyaniline [44], and 100 S/cm for sulfuric acid doped PPV [45] to 50 S/cm for iodine-doped poly thiophene [46]. The above listed conductivities refer to the unsubstituted polymers other substitution patterns can lead to different film morphologies and thus to a different electrical conductivity for the same class of conjugated polymer in the doped state. 

Intercalation of electroactive polymers such as polyaniline and polypyrrole in mica-type layered silicates leads to metal-insulator nanocomposites. The conductivity of these nanocomposites in the form of films is highly anisotropic, with the in-plane conductivity 10 to 10 times higher than the conductivity in the direction perpendicular to the film. Conductive polymer/oxide bronze nanocomposites have been prepared by intercalating polythiophene in V2O5 layered phase, which is analogous to clays. °° Studies of these composites are expected not only to provide a fundamental understanding of the conduction mechanism in the polymers, but also to lead to diverse electrical and optical properties. 

Depending on their structure, the polymers containing heterocycles have various applications. For example, poly(furfuryl alcohol) is used in composite materials with fillers such as sand and concrete, in copolymers with formaldehyde, etc. Some of the polymers from this group have special properties such as good electrical conductivity (after appropriate doping). Among these polymers are poly(thiophene-2,5-diyl) and particularly polypyrrole, CAS 109-97-7, (usually in carbon black doped with an organic acid anion). The structure of this polymer is shown below ... 

All experiments showed that the corresponding polymers precipitated from solution. After filtration and washing with hot water, polypyrrole and poly(EDT) were obtained as dark powders in their oxidized state. Conductivity measurements showed that these materials have the same electrical properties (10-100 S cur1) as conventionally prepared polypyrrole or poly(EDT) [27,28],... 

In addition to the above-mentioned conventional polymers, several interesting developments have taken place in the preparation of nanocomposites of MMT with some specialty polymers including the N-heterocyclic polymers like poly (N-vinylcarbazole) (PNVC) [32, 33], polypyrrole (PPY) [34, 35], and polyaromatics such as polyaniline (PANI) [36-38]. PNVC is well known for its high thermal stability [39] and characteristic optoelectronic properties [40-43]. PPY and PANI are known to display electric conductivity [44-46]. Naturally, composites based on these polymers should be expected to lead to novel materials [47,48]. 

Polypyrrole is one of a series of heterocyclic polymers which has attracted much attention due to its characteristic electric and electronic properties. However, there are some problems relating to the physical and material properties associated with its structure. The fundamental structural formulae shown in Fig. 16.5 have been generally proposed for the structures of dedoped and doped polypyrroles, where the aromatic form corresponds to the dedoped state and the quinoid form corresponds to the doped state [9-11]. However, the actual structure appears to be more complicated. At present the exact structure is not known because the polymer is amorphous and insoluble. Consequently, various structures have been proposed for polypyrrole [10]. 

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