Linear polyglycidols of high molar masses were prepared by the monomer-activated anionic polymerization of the corresponding protected monomers, ethoxyethyl glycidyl ether and tert-butyl glycidyl ether, using a system composed of tetraoctylammonium bromide as initiator and triisobutylaluminum as monomer activator. The aluminic compound was used in 1.5-5-fold excess compared to the initiator. Linear poly(ethoxyethyl glycidyl ether) and poly(tert-butyl glycidyl ether), with narrow chain dispersity and controlled high molar masses, up to 85 000 g/mol, were prepared at 0 °C in a few hours. Deprotection of hydroxyl functions by acidic treatment of the polymers was shown to proceed quantitatively and cleanly affording the corresponding linear polyglycerol and validating the use of these protecting groups. The copolymerization of protected glycidols with propylene oxide and butene oxide was also investigated with the goal to broaden the scope of this synthetic approach to various polyethers and copolyethers.

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International audiencePoly(allyl glycidyl ether) and poly(allyl glycidyl etherco- epichlorohydrin) were prepared by monomer-activated anionic polymerization. Quantitative and controlled polymerization of allyl glycidyl ether (AGE) giving high molar mass polyether was achieved in a few hours at room temperature in toluene using tetraoctylammonium salt as initiator in presence of an excess of triisobutylaluminum ([i-Bu3Al]/[NOct4Br] ¼ 2 4). Following the same polymerization route, the copolymerization of AGE and epichlorohydrin yields in a living-like manner gradient-type copolymers with controlled molar masses. Chemical modification of the pendant allyl group into cyclic carbonate was then investigated and the corresponding polymers were used as precursors for the isocyanate-free synthesis of polyurethane networks in presence of a diamine. Formation of crosslinked materials was followed and characterized by infrared and differential scanning calorimetry