Linear High Molar Mass Polyglycidol and its Direct α‐Azido Functionalization

Abstract

Abstract Summary: Linear polyglycidols with narrow chain dispersity and controlled high molar masses were prepared in a few hours by monomer‐activated anionic polymerization of protected monomers, ethoxyethyl glycidyl ether and tert ‐butyl glycidyl ether, using a system composed of tetraoctylammonium bromide as initiator and triisobutylaluminum, used in 1.5 to 5‐fold excess compared to the initiator, as co‐initiator and monomer activator. This synthetic approach was shown to give various polyglycidol‐based copolyethers in particular with propylene oxide or butene oxide. α‐Azido,ω‐hydroxy‐poly(ethoxyethyl glycidyl ether) and other polyethers were directly prepared when tetrabutylammonium azide was used as initiator. Size exclusion chromatography and matrix‐assisted laser desorption/ionization time‐of‐flight characterizations as well as “click” reactions were used to demonstrate the efficiency of the functionalization.