Macromolecules, Vol.35, No.19, 7293-7300, 2002
Intrinsically conducting polymer networks of poly(thiophene) via solid-state oxidative cross-linking of a poly(norbornylene) containing terthiophene moieties
Herein we describe the preparation of intrinsically conducting poly(thiophene) via two different routes: solution- and solid-state cross-linking of terthiophene moieties. The solution-state crosslinking of terthiophene moieties was performed using conventional electrochemical polymerization in which insoluble cross-linked polymer was precipitated onto the electrode from electrolyte solution of the monomer by oxidative coupling of terthiophene units in the monomer, 5-norbornene-endo-2,3-bis(methylene-3'-[2,2':5',2"]-terthiophene acetate). In the alternative route, a precursor polymer, poly(norbornylene), prepared from the ring-opening metathesis polymerization (ROMP) of 5-norbornene-endo-2,3-bis(methylene-3'-[2,2':5',2"]-terthiophene acetate), was coated on either a conducting or insulating, surface, and then the terthiophene units were cross-linked to form intrinsically conductive polymer (ICP) via electrochemical and chemical oxidation, respectively. More highly.. conjugated ICP was observed by performing oxidative cross-linking of the polymer in the solid state, in contrast to the cross-linked intrinsically conducting polymer prepared via electrochemical polymerization of 5-norbornene-endo-2,3-bis(methylene-3'-[2,2':5',2"]-terthiophene acetate) from solution. Electrical conductivities for the polymers obtained via solid-state chemical oxidative cross-linking were on the order of 1 x 10(-3) S/cm.