The condensation of a mixture of dimethyl carbonate (DMC) and the phthalate derivatives (dimethyl terephthalate, dimethyl isophthalate, and dimethyl phthalate) with 1,4-butanediol (BD), using a sodium alkoxide catalyst, generated high-molecular-weight poly(1,4-butylene carbonate-co-aromatic ester)s with Mn values of 50000−120000. The subsequent addition of polyols (BD, glycerol propoxylate, 1,1,1-tris(hydroxymethyl)ethane, or pentaerythritol) chopped the generated high-molecular-weight polymers to afford macrodiols or macropolyols with facile control of their molecular weight (Mn, 2000−3000) and unique chain topological composition. Macropolyols prepared by chopping poly(1,4-butylene carbonate-co-terephthalate) were waxy in nature, whereas those containing isophthalate and phthalate units were instead oily. The glass transition temperatures observed for the macropolyols increased from −50 to −30 °C upon increasing the proportion of aromatic ester units, and the viscosity of the oily compounds increased on incorporating the aromatic ester units. DMC is a benign chemical produced from CO2; phthalate derivatives are also inexpensive chemicals that can be produced on a large scale. The macropolyols synthesized by this chopping method may have potential applications in the polyurethane industry.
