Mechanism and kinetics of polycarbonate synthesized from isosorbide: Identification on the reactivity of terminal groups

Abstract Challenges in the mechanistic and kinetic study on the polymerization with multiple functional monomers hinder the scale‐up for the controllable reaction process. Herein, poly (isosorbide carbonate) synthesized from isosorbide (ISB) was employed to investigate the reaction behavior of functional monomers during polymerization. DFT calculations not only determined the energetically preferable pathways but also provided explanations for the significant differences between terminal groups at the molecular level. Subsequently, the characteristic absorption bands were detected from 1000 to 1100 cm −1 for hydroxyls on ISB, providing a quantitative measure for asymmetric hydroxyls. The reaction network indicated that the reactivity was dominated by the types of terminal groups instead of the chain length. Thereafter, a functional group model with six kinetic parameters was built, acting a crucial role in reaction control and reactor design. This method can be promoted to other functional monomers, conducing to the industrialization of high‐performance polymers.