Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salen)Co(III) complex tethering four quaternary ammonium salts

The (salen)Co(III) complex 1 tethering four quaternary ammonium salts, which is a highly active catalyst in CO(2)/epoxide copolymerizations, shows high activity for propylene oxide/phthalic anhydride (PO/PA) copolymerizations and PO/CO(2)/PA terpolymerizations. In the PO/PA copolymerizations, full conversion of PA was achieved within 5 h, and strictly alternating copolymers of poly(1,2-propylene phthalate)s were afforded without any formation of ether linkages. In the PO/CO(2)/PA terpolymerizations, full conversion of PA was also achieved within 4 h. The resulting polymers were gradient poly(1,2-propylene carbonate-co-phthalate)s because of the drift in the PA concentration during the terpolymerization. Both polymerizations showed immortal polymerization character; therefore, the molecular weights were determined by the activity (g/mol-1) and the number of chain-growing sites per 1 [anions in 1 (5) + water (present as impurity) + ethanol (deliberately fed)], and the molecular weight distributions were narrow (M(w)/M(n), 1.05–1.5). Because of the extremely high activity of 1, high-molecular-weight polymers were generated (M(n) up to 170,000 and 350,000 for the PO/PA copolymerization and PO/CO(2)/PA terpolymerization, respectively). The terpolymers bearing a substantial number of PA units (f(PA), 0.23) showed a higher glass-transition temperature (48 °C) than the CO(2)/PO alternating copolymer (40 °C).