Polyelectrolytes with polypyrrole

If the dopant anion (A ) is small and mobile (eg. Cl ) and the polymer has a high surface area to volume ratio, then upon reduction the anion will be efficiently ejected from the polymer. However, extensive studies with polypyrroles have shown [4] that if the dopant is large and immobile (eg. if A" is a polyelectrolyte such as polystyrene sulfonate) then an electrically induced cation exchange process occurs, according to Eqn. 3,... 

More recently, it has been foimd that anions such as polyelectrolytes and surfactant-like anions, e.g., dodecylbenzenesulfonate (DBSA), can be inserted directly into polypyrrole products during polymerization in competition with anions arising from the oxidant. This very useful development will be discussed later in a section dealing with polypyrrole processability. 

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). 

By electropolymerization of pyrrole in solvents containing polyelectrolytes such as potassium polyvinylsulfate, it is possible to prepare films of polypyrrole with polymeric counterions which have good conductivity (1-10 S cm-1) and strength (49 MPa) 303 304,305). Such a material could be used reversibly to absorb cations in an ion exchange system. Pyrrole has also been electrochemically polymerized in microporous polytetrafluoroethylene membranes (Gore-tex), impregnated with a perfluorosulphonate ionomer 3061. 

Furthermore, porous CPs (e.g., polypyrrole, polyanUine) films have been used as host matrices for polyelectrolyte capsules developed from composite material, which can combine electric conductivity of the polymer with controlled permeability of polyelectrolyte shell to form controllable micro- and nanocontainers. A recent example was reported by D.G. Schchukin and his co-workers [21]. They introduced a novel application of polyelectrolyte microcapsules as microcontainers with a electrochemically reversible flux of redox-active materials into and out of the capsule volume. Incorporation of the capsules inside a polypyrrole (PPy) film resulted in a new composite electrode. This electrode combined the electrocatalytic and conducting properties of the PPy with the storage and release properties of the capsules, and if loaded with electrochemical fuels, this film possessed electrochemically controlled switching between open and closed states of the capsule shell. This approach could also be of practical interest for chemically rechargeable batteries or fuel cells operating on an absolutely new concept. However, in this case, PPy was just utilized as support for the polyelectrolyte microcapsules. 

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