Ab initio and experimental study on thermally degradable polycarbonates: Effect of structure on reactivity

V. Van Speybroeck, M. Waroquier, Y. Martele, E. Schacht
International Journal of Quantum Chemistry
91(3), 363-368


The thermal degradation process of some new synthesized polycarbonates is studied both from theoretical and experimental points of view to obtain microscopic insight into the factors that govern the reaction rates. Ab initio density functional theory calculations are performed on a set of carbonates, which are model systems for the polycarbonates. Kinetic parameters are determined by transition-state theory and compared with experimental-derived degradation temperatures. The study as presented here gives evidence of the existence of a correlation between these degradation temperatures and the reaction rates resulting from static ab initio calculations on small model systems that are representative for the active area of the degradation process. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2003