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

A sequential and mild approach towards 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 step-wise construction of different PLDC polymers using PLC as a synthetic intermediate with molecular weights of up to 15.3 kg/mol and tunable Tg´s of up to an unprecedented 180ºC using a commercially available mixture of cis/trans (+)-LO.