Access to Biorenewable Polycarbonates with Unusual Glass-Transition Temperature (Tg) Modulation

A sequential and mild approach toward the synthesis of poly(limonene)dicarbonate (PLDC) has been developed using readily available limonene oxide (LO) and CO2 as renewable reagents and an air-stable Al(III) complex as catalyst for the alkene-rich poly(limonene)carbonate (PLC). The developed sequence allows for the stepwise construction of different PLDC polymers, using PLC as a synthetic intermediate with molecular weights of up to 15.3 kg/mol and tunable glass-transition temperature (Tg) values of up to an unprecedented 180 °C using a commercially available mixture of cis/trans (+)-LO.