Electrochemical Polymerization of 1,2‐Dithiolane Derivatives at Room Temperature

Abstract Recently, 1,2‐dithiolanes derived polydisulfides have prompted growing research interests. An innovative polymerization method with convenient operation under mild conditions is needed for improving monomer conversion, polymerization degree, and bulk performance. Here, we report an electrochemically initiated ring‐opening polymerization (ROP) of thioctic acid (TA) monomers and its derivatives at room temperature, with high monomer conversion and polymerization degree. The resulting polymer exhibits potential as a transparent and vibration‐damping coating. Electrochemical oxidation was the key step for initiating the rapidly polymerization and could completely circumvent the use of chemical initiators or harsh conditions. Cyclic voltammetry experiments identified the oxidation of TA at anode accompanying with an absorption‐controlled one‐electron transfer process. Together with density functional theory calculations, we proposed a cationic radical‐initiated polymerization process. This unique electrochemical polymerization strategy was simple, rapid, efficient, and applicable for diverse TA‐derived monomers.