Thermally induced redistribution and degradation of bisphenol-A polycarbonate fractions in open and closed systems

Thermally induced chain-scission and redistribution reactions in as-polymerized and fractionated bisphenol-A polycarbonate (PC) materials made by melt-transesterification and interfacial polymerization were studied at temperatures between 200 and 300 degreesC in open systems, where volatile reaction products are continuously removed, and in closed systems, where these products are retained. Under the applied conditions, PC made via interfacial polymerization shows no measurable susceptibility towards redistribution. This is the result of an extremely low concentration of hydroxyl end-groups. Upon similar thermal treatment, PC made by melt-transesterification undergoes fast redistribution which leads to post-condensation in open systems and strong changes of molecular weight distributions (MWDs) for fractions in all cases. Redistribution effects were visualized through changes in the MIND of mixed fractions. The initial stages of redistribution were simulated using a Monte Carlo method based on a random sampling technique. From comparison between experimental and simulation results, it can be concluded that approximately half a percent of all carbonate linkages is involved in a redistribution reaction per minute at 250 degreesC for the studied samples. (C) 2002 Elsevier Science Ltd. All rights reserved