ELECTROCHEMICALLY MEDIATED ATOM TRANSFER RADICAL POLYMERIZATION

摘要

Electrochemical reduction of an exemplary ATRP catalyst, C11Br2/Me6TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form Cu1Br2/Me6TREN, within the reaction medium. Unprecedented control over the polymerization kinetics can be attained through electrochemical methods by modulating the magnitude of the applied potential allowing polymerization rate enhancement or retardation. Additional polymerization control is gained through electrochemical “dials” allowing polymerization rate enhancements achieved by larger applied potentials and the ability to successfully switch a polymerization “on” and “off between dormant and active states by application of multistep intermittent potentials.

主权项

1. A polymerization process, comprising:
polymerizing free radically (co)polymerizable monomers in the presence of a polymerization medium initially comprising: at least one transition metal catalyst that can participate in a redox reaction; and an initiator comprising one or more redox transferable atoms or groups; wherein the molar ratio of the oxidation states of the transition metal catalyst are adjusted, controlled, and/or maintained by electrochemistry.