Abstract
Carbon dioxide (CO2) is a thermodynamically and kinetically stable compound that leaves little option but to resort to organometallic complexes for promoting reactions such as its copolymerization with epoxides. These organometallic complexes function by coordination-insertion of CO2 for the mechanism of their (co)polymerization with epoxides and involve generally either transition metals (mainly Cr, Co, Zn) or earthabundant main group metals (Al, Mg). In this study a non-coordinating route is investigated based on the use of mere alkoxydes for the initiation of the copolymerization of CO2 and epoxides and on alkyl aluminum for the activation of epoxides. This anionically-driven copolymerization of CO2 and epoxides is versatile enough to allow not only the straightforward synthesis of perfectly alternating polycarbonates but also the easy derivation of poly(ether-cocarbonate)s of different compositions or the facile preparation of block copolymers of polystyrene-b- polycarbonate type by sequential polymerization.