Visualization of the crucial step in SET-LRP

Aqueous SET-LRP catalyzed with “in situ” generated Cu(0) demonstrates surface mediated activation and bimolecular termination

“…6a). 43,46,89 As a result, the absorption spectra at 0°C (Fig. 6a) could not be normalized to zero at any wavelength.…”

Cu(0)-Mediated Living Radical Polymerization: A Versatile Tool for Materials Synthesis

“…Polar solvents, such as DMSO and H 2 O, favor the disproportionation of Cu I Br and present a first order rate of polymerization maintaining very high end-group functionality up to 100% conversion. 146 86 and tert-butanol (tBuOH), 61 have also all shown excellent compatibility with SET-LRP and disproportionation resulting in the preparation of well-defined polymers with narrow MWDs. Any binary mixtures of disproportionating solvents can also be utilized for the synthesis of well-defined polymers via SET-LRP (H 2 O/MeOH mixtures, 80 70,110,153 which provide effective SET-LRP media for both hydrophobic and hydrophilic acrylates and methacrylates with excellent dispersities and very high retention of chain-end functionality.…”

PSt-b-PU-b-PSt copolymers using tetraphenylethane-urethane macroinitiator through SARA ATRP

“…SARA ATRP, has Cu I /Cu II reactions as the major activation/deactivation ones, with Cu 0 acting as a supplemental activator of alkyl halides and a reducing agent for excess Cu II , and limiting disproportionation of Cu I ( Figure 1) [15,16]. Meanwhile, Percec group has proposed a single electron transfer living radical polymerization (SET-LRP) mechanism [18][19][20][21][22], which postulates Cu 0 as the major activator of alkyl halides, Cu II as the major deactivator and assumes that Cu I not participating in activation reactions and instead undergoing very rapid disproportionation to Cu 0 and Cu II [19]. Taking into account the Matyjaszewski's researches [17,23,24] it can be stated that the SARA ATRP mechanism is correct.…”