| The precision synthesis of covalent polymers with well-defined compositions, architecture and perfect structural fidelity has been of great interest in the field of polymer chemistry. Living radical polymerization is considered as one of the most rapidly developing areas in polymer science. It has provided synthetic polymer chemists with methods and strategies for the preparation of complex macromolecule structures otherwise inaccessible by conventional polymerization methods.;Single-electron transfer living radical polymerization (SET-LRP) has emerged as a powerful technique for the ultrafast synthesis of functional polymers under mild conditions with high end-group fidelity. The work presented here provides mechanistic insights into the Cu(0) surface-mediated activation process, and elucidation of the effects of initiator structure, ligand structure and concentration, solvent polarity and extent of disproportionation on the kinetics and molecular weight control of SET-LRP. Additionally, an in-depth structural analysis of the polymers prepared by SET-LRP imparts further evidence for the critical role of the solvent/ligand-mediated disproportionation of CuX in the proposed mechanism of SET-LRP. Finally, SET-LRP was utilized for the synthesis of perfectly functional polymers in the presence and absence of air, and of functional hydrophilic polymers in protic and dipolar aprotic solvents. |
