NMP of styrene in batch and CSTR at elevated temperatures: Modeling experimental trends

Nitroxide-mediated polymerization (NMP) is conducted in batch and in a continuous stirred-tank reactor (CSTR) at temperatures up to 200 degrees C using a thermally stable nitroxide. A kinetic model was developed using the Predici (R) software package to further understand the experimental trends under batch and continuous operation. Using the estimated activation/deactivation rate coefficients from the batch polymerization, the model predicts that a significant amount of alkoxyamine is exiting the CSTR under steady state conditions, consistent with a low molecular weight peak found experimentally. The predicted outlet concentration of alkoxyamine at steady state is decreased by increasing the temperature and residence time in the reactor. Batch chain extension of the polymer produced in the CSTR supports the potential for continuous production of block copolymers. (C) 2016 Elsevier Ltd. All rights reserved.