Electrochemistry provides easily tunable parameters for the preparation of well-defined polymers in a spatiotemporal controlled manner under mild conditions. This work discusses the requisites for an electrochemically mediated reversible addition–fragmentation… Click to show full abstract
Electrochemistry provides easily tunable parameters for the preparation of well-defined polymers in a spatiotemporal controlled manner under mild conditions. This work discusses the requisites for an electrochemically mediated reversible addition–fragmentation chain-transfer (eRAFT) polymerization, in which electrochemical stimuli are used to reduce the RAFT agent, either directly or in the presence of a mediator. The redox properties of several RAFT agents were investigated by cyclic voltammetry and correlated to their structures. The direct electrolysis of RAFT agents in the presence of a monomer caused the loss of RAFT agents, thus leading to uncontrolled polymerizations. These issues could partially be overcome by using a mediator that shuttles the electrons from the electrode to the RAFT agent in solution. Several compounds were tested to define the characteristics of suitable mediators.
               
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