Intermolecular radical 1,2-addition of the BlocBuilder MA alkoxyamine onto activated olefins: a versatile tool for the synthesis of complex macromolecular architecture

Abstract

International audienceThis review described the potential of the intermolecular radical 1,2-addition from the commercially available BlocBuilder MA alkoxyamine onto activated olefins to synthesize either new functionalized alkoxyamines or various macromolecular architectures. Following this approach, diblock, triblock copolymers, star polymers and hybrid materials are then easily prepared. The various applications of such architectures will be briefly reviewed. Interestingly this new synthetic tool widely expands the range of complex macromolecular architectures which could be obtained by the nitroxide-mediated polymerization (NMP) process

Free‐radical polymerization upon near‐infrared light irradiation, merging photochemical and photothermal initiating methods

“…This has already been reported in ref. and the use of BlocBuilder MA for the nitroxide‐mediated Polymerization has been detailed. However, it is fully possible to use more “regular” thermal initiators in our combined photochemical/photothermal approach.…”

On the structure–control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation

“…24,25 Alkoxyamines 13-16 were prepared by 1,2 intermolecular radical addition onto the corresponding olefins. 26 This synthetic route was shown to be very efficient for the preparation of secondary functionalized SG1-based alkoxyamines that can also act as precursors for macromolecular engineering. The penultimate unit effect (PUE) is known to drastically increase the dissociation rate constant of alkoxyamines 13-16 due to the Scheme 3 Structure of the different amide-functionalized SG1-based alkoxyamines synthesized and evaluated in this study.…”

Synthesis of Narrow Molecular Weight Distribution Copolymers for ArF Photoresist Materials by Nitroxide Mediated Polymerization

“…In addition, tight control over molecular weight distribution and excellent retention of chain end fidelity by SG1‐based NMP were also demonstrated in bulk, water‐borne (mini)emulsion and ionic liquids . Further, SG1‐based NMP has also been successfully applied to the synthesis of star‐shaped polymers, amphiphilic block copolymers, and graft copolymers …”