Quasilinear Polyglycidols by Triethyborane-Controlled Anionic Polymerization of Unprotected Glycidol

The synthesis of linear polyglycidol by direct homopolymerization of unprotected glycidol remains a big challenge due to the inimer nature of this monomer. In this study, quasilinear polyglycidols (PG)s with ultralow degree of branching (DB) could be synthesized through anionic polymerization of glycidol carried out in the presence of triethylborane (TEB). PGs with DB ≤ 0.10, and molar masses up to 40 kg/mol could be indeed obtained using mono- or trifunctional ammonium carboxylates as initiator and under slow monomer addition conditions. The synthesis of degradable PGs through ester linkages by copolymerization of glycidol with anhydride is also described. PG-based amphiphilic di- and triblock quasilinear copolymers were also derived. The role played by TEB is discussed and a polymerization mechanism is proposed.