Reaction Network Identification in High-Temperature Polymerization of N-Butyl Acrylate: a Simultaneous Parameter Estimation Approach

摘要

Increasingly higher average reaction temperature used in many industrial-scale polymerization reactors has motivated improvement in existing 'low-temperature' polymerization reactor models. The inability of the existing mechanistic models in predicting the dynamics of high-temperature polymerization processes is due to the significant contribution of secondary reactions at the higher temperatures (Quan et al., 2002; Peck and Hutchinson, 2004). At lower temperatures, these secondary reactions contribute little to the overall rate of polymerization and are usually ignored. For example, 1D-NMR and FT-MS studies in high-temperature polymerization of ethyl acrylate point to the creation of a slower intermediate radical which can undergo scission to form terminal double bonds (TDB) or propagate further to create chain-branching (Quan et al., 2002, 2005; Peck and Hutchinson, 2004).