Polyethers, derived from epoxides, are important for a range of applications including pharmaceutical formulations and membranes for carbon capture. Access to new polyether materials could advance these applications and also address other areas of growing technological challenge. Building off the previous success of mono(µ-alkoxo)bis(alkylaluminum) (MOB) initiator/catalysts which displayed rapid kinetics for epoxide polymerizations, it is now possible to independently control molecular weight and end group functionality by decoupling the initiation and catalysis functionalities of the MOB species. This new class of catalysts consist of a simple Lewis pair between an alkylamine and alkylaluminum. X-ray diffraction crystallography was used to determine the structure of the catalysts and associated initiators. End group control was verified with electrospray ionization mass spectrometry. The rate of polymerization was tuned by catalyst identity and concentration. Kinetic studies of the polymerization of allyl glycidyl ether monomer suggested that the rate was strongly dependent on catalyst concentration. A transition from 0th-order to 1st-order kinetics in monomer was observed with increasing catalyst concentration. With a new understanding of N-Al catalyzed polymerization kinetics, a simple and versatile tool for new polyether materials design has been developed.

Design and synthesis of functional polyethers using the N-Al adduct catalysts

2019 Spring National Meeting

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