Amphiphilic Block Copolymer from Hydroxyl‐Terminated Polymers Functionalized with TEMPO. A New Synthetic Method Using Oxoammonium Salt

Abstract

AbstractA simple approach for the end‐functionalization of hydroxyl‐terminated polymers with nitroxide moieties using oxoammonium salts (OS) is presented. The functionalization is carried out using only one synthetic pathway in which high levels of functionalization (90%) are found. A mechanism for the functionalization with TEMPO moieties using OS is proposed in which the formation of peroxide groups is suggested. The structures of the functionalized polymers are characterized in detail by 1H NMR, 13C NMR, DQF‐COSY, and HETCOR. Bifunctional macroalkoxyamines are used to demonstrate how to extend the polymer chain for the synthesis of amphiphilic triblock copolymers by polymerizing St in a second block mediated by a nitroxide radical which provides the block length control. magnified image