Polypyrrole substituted

Biswas and Roy [118,119] studied the degradation and stability of chemically prepared polypyrrole substituted by phthalic anhydride (PPY-PhAn) and pyromellitic dianhydride (PPY-PMDA) by using a thermal analyser and IR spectroscopy. They found that the chemical modification enhanced the thermal stability of the modified polypyrrole as compared with... 

In contrast to the N-substituted polypyrroles, substitution at the 3-position results in polymers with a similar oxidation potential as the unsubstituted pyrrole and a higher conductivity. Some examples include methyl substituted bipyrroles (25a-c) [96], poly(3-hydroquinonylpyrrole) (26) [99], and poly(3-alkylsul-fonate pyrrole)s (27a-c) [100]. Unfortunately, because 3-substitution of the pyrrole ring is synthetically demanding and the resulting polymer shows a higher degree of sensitivity to air in the neutral state, more focus has been placed on iV-substitution as opposed to 3-substitution of the pyrrole monomer unit. 

Significant variations in the properties of polypyrrole [30604-81-0] ate controlled by the electrolyte used in the polymerization. Monoanionic, multianionic, and polyelectrolyte dopants have been studied extensively (61—67). Properties can also be controlled by polymerization of substituted pyrrole monomers, with substitution being at either the 3 position (5) (68—71) or on the nitrogen (6) (72—75). An interesting approach has been to substitute the monomer with a group terminated by an ion, which can then act as the dopant in the oxidized form of the polymer forming a so-called self-doped system such as the one shown in (7) (76—80). 

In all cases of electrochemicaHy or chemically polymerized unsubstituted polypyrrole, the final polymer is intractable in both the conducting and insulating forms. In contrast, a broad number of substituted polythiophenes have been found to be processible both from solution and in the melt. The most studied of these systems ate the poly(3-alkylthiophenes) (P3AT). 

Poly(phenylenepyrazoles), 5, 300 Polypyrazoles, 5, 300 N-substituted, 5, 300 Polypyrazolines, 5, 300 Poly(pyrazol-l-yl) borates as ligands, 5, 225, 235 Polypyrroles applications, 4, 376 Polypyrrole tetrafluoroborate conductors, 1, 355 Polysaccharides as pharmaceuticals, 1, 152 Poly-2,5-selenienylenes applications, 4, 971 Polysilacyclopentanes, 1, 609 Polysufides macrocyclic... 

Figure 13. (a) Substituted polypyrrole, (b) self-doped polypyrrole, (c) heteroaromatic polymer showing the monomer unit, (d) composite polypyrrole-polyelectrolyte, and (e) hybrid material. (Polyaniline macroion photo supplied by Gomez-Romero and M. Lira.)... 

If the film is nonconductive, the ion must diffuse to the electrode surface before it can be oxidized or reduced, or electrons must diffuse (hop) through the film by self-exchange, as in regular ionomer-modified electrodes.9 Cyclic voltammograms have the characteristic shape for diffusion control, and peak currents are proportional to the square root of the scan speed, as seen for species in solution. This is illustrated in Fig. 21 (A) for [Fe(CN)6]3 /4 in polypyrrole with a pyridinium substituent at the 1-position.243 This N-substituted polypyrrole does not become conductive until potentials significantly above the formal potential of the [Fe(CN)6]3"/4 couple. In contrast, a similar polymer with a pyridinium substituent at the 3-position is conductive at this potential. The polymer can therefore mediate electron transport to and from the immobilized ions, and their voltammetry becomes characteristic of thin-layer electrochemistry [Fig. 21(B)], with sharp symmetrical peaks that increase linearly with increasing scan speed. 

Due to its electronic conductivity, polypyrrole can be grown to considerable thickness. It also constitutes, by itself, as a film on platinum or gold, a new type of electrode surface that exhibits catalytic activity in the electrochemical oxidation of ascorbic acid and dopamine in the reversible redox reactions of hydroquinones and the reduction of molecular oxygen iV-substituted pyrroles are excellent... 

Table 1. N-substituted pyrroles employed in the preparation of redox-Modified polypyrrole films on electrodes...

Table 3. Electrochemical data for AT-phenyl-substituted polypyrroles (all data from cyclic voltammetry using 0.1 M Et4NBF4 in acetonitrile exceptab).

Furthermore, the utilization of preformed films of polypyrrole functionalized by suitable monomeric ruthenium complexes allows the circumvention of problems due to the moderate stability of these complexes to aerial oxidation when free in solution. A similar CO/HCOO-selectivity with regards to the substitution of the V-pyrrole-bpy ligand by an electron-with-drawing group is retained in those composite materials.98 The related osmium-based redox-active polymer [Os°(bpy)(CO)2] was prepared, and is also an excellent electrocatalyst for the reduction of C02 in aqueous media.99 However, the selectivity toward CO vs. HCOO- production is lower. 

The other important electrochromic polymers are the polypyrroles and polythiophenes, obtained by polymerisation of the parent pyrrole and thiophene or, more importantly, their 3,4-substituted derivatives. The most widely studied of these two classes of polymers in electrochromic outlets are the poly thiophenes, which are readily synthesised by the reaction of the substituted monomer with FeClj in chloroform solution. The colour change properties of a variety of poly thiophenes in the presence of a counter-ion are shown in Table 1.14. ... 

Anodic oxidation of pyrrole and N-substituted pyrroles results in the formation of polypyrroles in an oxidized state, which can be useful for the preparation of conducting organic polymers.185-188 Oxidation of 2,5-di-substituted pyrroles produces soluble products and no layer of polymers.187 One of the proposed applications of such a layer of conducting polymer is the protection of semiconductor electrodes from photocorrosion.189-191... 

Thus it appears that non-substituted pyrrole at the 2,5 positions is highly recommended to produce good quality polypyrrole (PPy). See Figure 1. Besides, conducting PPy needs to be doped to stabilize the generated positive charges which is equivalent to say that it requires the presence of anions. In this sense pyrrole/pyrrolyl t)5 coordination to a metal may be... 

In the synthesis of ferrocene-functionalized polypyrrole systems, numerous derivatives are readily obtained by substitution at either the 3-position of the ring or on the nitrogen of the pyrrole prior to polymerization. It was reported that polymers with both metallic properties and enhanced solubility may be synthesized by judicious derivatization and choice of polymerization conditions, such as a variety of processing solvents [67, 68]. 

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. 

Both electrochemical and chemical oxidation have been used to produce 3-substituted alkylsulfonated pyrroles [106]. Electrochemical polymerisation was achieved using acetonitrile as solvent to form a solid deposit on the electrode. Alternatively, FeCl3 was used as oxidant. Conductivities in the range 0.001-0.500 S cm were obtained, with lower conductivity products obtained from chemical polymerisation. Others [107,108] have prepared homopolymers and copolymers of polypyrroles with alkyl sulfonate groups attached via the N-group. This N-group substitution decreases the polymers inherent conductivity. 

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