Anionic ring-opening polymerization of propylene oxide, initiated with protonated phosphazene alkoxides and based on monomer activation with a Lewis acid, is investigated. Alcohols bearing one or several protected hydroxyl groups, namely 1,2-isopropylideneglycerol, 1,2:3,4-di-O-isopropylidene-Dgalactopyranose and poly(propylene glycol), are firstly deprotonated with a phosphazene base. Their combination with triisobutylaluminum enables quantitative and controlled synthesis of poly(propylene oxide) in a very short time (hours), at room temperature and in hydrocarbons. The chain-ends determination showed a main population initiated by the protonated phosphazene alkoxide. A population coming from the residual transfer to monomer is also observed but in very low intensity. Molar masses of 80 000 g mol À1 with relatively narrow dispersity could be prepared. After deprotection of protected hydroxyl functions, tri-and penta-hydroxy telechelic poly(propylene oxide) were obtained. Dihydroxy telechelic polymers of high molar masses are also rapidly and directly synthesized from poly (propylene glycol).
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