Synthetic polymers are now an essential part of numerous and varied objects and materials in our everyday life. In the last decades, polymer science has developed into a modern and multidisciplinary research field thanks to fundamental discoveries and achievements. Initially devoted to structural applications, polymers are indeed increasingly involved in higher-value-added functional materials from electronic-, optical- and biomedical-related areas. This explains why polymer science is now considered as an essential and innovative research field from both academia and industry.
Among the crucial contributions witnessed in polymer science is the development of living polymerization techniques, which allows tailor-made macromolecules to be synthesized. From the conceptual point of view, a living polymerization can be seen as a chain polymerization that proceeds without the occurrence of chain transfer and termination events, through the establishment of a dynamic equilibrium between active and dormant species. Initially materialized by Szwarc in 1956 [1] this methodology indeed opened the door to well-defined polymers with precise and predetermined molar masses, compositions, topologies and functionalities. However, those living polymerization techniques exhibit two main drawbacks: (i) the impossibility to polymerize a wide range of functionalized vinylic monomers due to the incompatibility of the active center with certain functional groups and (ii) the requirement of stringent reaction conditions; especially the use of chemically ultrapure reagents as well as the absolute removal of air and of traces of water.
Until 15 years ago, living anionic and cationic polymerizations were the only available methods to reach a high degree of structural and compositional homogeneity of polymers before recent developments in macromolecular synthesis provide a new synthetic tool to easily achieve complex macromolecular architectures: controlled/living radical polymerization (CLRP). This general term gathers several novel free-radical polymerization techniques that enable a high degree of control to be reached. Indeed, free-radical polymerization differs from ionic polymerization by: (i) its relative ease-of-use (only dissolved oxygen has to be eliminated); (ii) the broad range of vinylic monomers which can be polymerized by a radical mechanism and (iii) the numerous processes that can be implemented (bulk, solution, emulsion, dispersion, etc.). However, the main limitation of free-radical polymerization is the total lack of control over the molar mass, the molar mass distribution (MMD), the chain-end functionalities and the macromolecular architecture. Therefore, bringing together the ease of use of free-radical polymerization with the high standard of control provided by living ionic polymerization, within a single polymerization process, simply brought about a revolution in the field of macromolecular synthesis.
In this view, various CLRP methods have been developed since the early 1980s, each of them being based on a different mechanistic approach and having encountered more or less success over the years. Basically, whatever the involved mechanism, their joint, key feature is the establishment of a dynamic equilibrium between propagating radicals, [Pradical dot], and various dormant species (i.e., end-capped, thus unable to propagate) throughout the polymerization process in order to decrease the occurrence of irreversible termination reactions to an extremely low level. The so-obtained equilibrium ( Fig. 1) is triggered and governed by thermal, photochemical and/or chemical stimuli. For the success of such an approach, a polymer chain should spend most of the polymerization time under its dormant state.