Electrochemical topological transformation of polysiloxanes

Coupling reactions between polymers are an important class of chemical modifications for changing, enhancing, and tuning the properties of polymeric materials. In particular, transformation of polymer topologies based on efficient, facile and less wasted coupling reactions remains a significant challenge. Here, we report coupling reactions based on electrochemical oxidation of 2,4,5-triphenylimidazole into a 2,4,5-triphenylimidazolyl radical and its spontaneous dimerization into hexaarylbiimidazole. Based on this chemistry, electrochemical topological transformation (ETT) and electrochemical chain extension have been realized with siloxane-based oligomers and polymers. Moreover, this approach enables one step ETT of star-shaped poly(dimethyl siloxane)s (PDMSs) into network PDMSs, running in an ionic liquid solvent and requiring no purification steps. Polymer–polymer coupling reactions using an excess amount of chemical oxidants are wasteful. Here the authors report an electrochemical route for chain extension and topological transformations of poly(dimethylsiloxane).