Catalyst residues severely impact the thermal stability and degradation mechanism of polycarbonates: How to turn a flaw into an opportunity

Three poly(cyclohexene carbonates) with molecular weights ranging from 4.9 to 9.4 kg/mol were synthesized from cyclohexene oxide and CO2 using macrocyclic phenolate dimetallic catalysts and purified by conventional purification procedure. A decrease in thermal stability of approximately 100 °C was observed in comparison to poly(cyclohexene carbonates) with similar molecular weights synthesized using salen metal catalysts. This decrease derives from the presence of traces of dimetallic catalyst which is able to promote the depolymerisation of poly(cyclohexene carbonate) to CO2 and cyclohexene oxide in contrast to the usual backbiting mechanism that leads to cyclic carbonate. The onset of the degradation can be precisely tuned by changing the amount of residual dimetallic catalyst or including species with functional groups that can reduce the availability of the catalytic centers. Therefore, the possibility of controlling the thermal stability of poly(cyclohexene carbonates) by varying the concentration of the catalyst and the surrounding chemical environment paves the way for the use of these polymers as components in self-sacrificial materials of interest for advanced applications.