<br/>A new class of aluminum based initiator for epoxide polymerizations is presented, which we call the trialkylaluminum adduct of (x) ethoxy-dialkylaluminum (TAxEDA), where x represents an interchangeable end group. The TAxEDA initiator is characterized as a mono-µ-oxo-dialuminum (MOD) species. TAxEDA can be synthesized in a single step with purification accomplished by direct crystallization from the reaction medium. The versatility of the new class of initiator was demonstrated by the polymerization and copolymerization of various functional monomers such as allyl glycidyl ether, epichlorohydrin, and propargyl glycidyl ether. Kinetic and mechanistic aspects of TAxEDA-initiated (co)polymerization were revealed using <i>in-situ</i> FTIR and NMR spectroscopy. We studied the effect of the TAxEDA structure on polymerization rate, livingness, and end group functionality. From this, we propose a mechanism that accounts for the living nature of the polymerization and both the stereo- and regiostructure of the resultant polymers. This new synthetic tool combines many of the advantages of traditional oxyanionic with other group 13 and transition metal approaches to the living polymerization of epoxides into well-defined, functional, polyether materials.

General, facile approach to epoxide polymerizations

254th National Meeting (2017)

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