Improving the Charge Conductance of Elemental Sulfur via Tandem Inverse Vulcanization and Electropolymerization.

The synthesis of polymeric materials using elemental sulfur (S) as the chemical feedstock has recently been developed using a process termed inverse vulcanization. The preparation of chemically stable sulfur copolymers was previously prepared by the inverse vulcanization of S and 1,3-diisopropenylbenzene (DIB); however, the development of synthetic methods to introduce new chemical functionality into this novel class of polymers remains an important challenge. In this report the introduction of polythiophene segments into poly(sulfur--1,3-diisopropenylbenzene) is achieved by the inverse vulcanization of S with a styrenic functional 3,4-propylenedioxythiophene (ProDOT-Sty) and DIB, followed by electropolymerization of ProDOT side chains. This methodology demonstrates for the first time a facile approach to introduce new functionality into sulfur and high sulfur content polymers, while specifically enhancing the charge conductivity of these intrinsically highly resistive materials.