Abstract

AbstractAll controlled radical polymerization (CRP) procedures rely on a dynamic and rapid equilibrium between dormant and active species. This equilibrium can be established through different mechanisms and all the resulting CRP processes have their own advantages and limitations. Therefore, it becomes interesting to investigate the possibility of combining CRP techniques to eliminate specific drawbacks of each individual procedure. Atom transfer radical polymerization (ATRP) with alkyl pseudohalides acting as initiators and chain transfer agents was developed for that purpose. The process relies on a dual mechanism involving both activationdeactivation and reversible additionfragmentation chain transfer (RAFT). This peculiar characteristic of ATRP with alkyl pseudohalides acting as chain transfer agents made it possible to overcome some of the limitations typically associated with conventional ATRP and RAFT polymerization as well as to prepare new responsive materials.

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