High Molar Mass Polycarbonate via Dynamic Solution Transcarbonation Using Bis(methyl salicyl) Carbonate, an Activated Carbonate

High molar mass polycarbonate is synthesized via a solution transcarbonation of bis(methyl salicyl) carbonate and bisphenol-A at temperatures between 60 and 160 °C without the removal of the condensate, allowing the incorporation of thermosensitive monomers into polycarbonate. Kinetic and equilibrium studies show that the polymerization is 20–30 times faster at 120 °C compared to 60 °C, whereas the equilibrium M_w increases from 11 × 10³ g mol⁻¹ at 120 °C to 16 × 10³ g mol⁻¹ at 60 °C. This polycondensation is characterized by very high equilibrium constants ranging from 0.8 × 10³ at 160 °C to 4.1 × 10³ at 60 °C, corresponding to standard enthalpies and entropies of polymerization: −19 kJ mol⁻¹ < ΔH⁰ < −11 kJ mol⁻¹ and 13 J mol⁻¹ K⁻¹ < ΔS⁰ < 28 J mol⁻¹ K⁻¹. Without removal of the condensate, the system is shown to be dynamic and completely reversible when changing the temperature. Good predictability of this polycondensation is reported, where only at very low starting monomer concentrations, the formation of cyclics leads to deviations from the predicted behavior.