Fundamental modeling in anionic polymerization processes

The anionic solution polymerization of butadiene was studied employing both batch and continuous reactor operations with n‐butyllithium (n‐BuLi) initiator, tetramethylethylenediamine (TMEDA) modifier, and hexane solvent. A model was proposed that described the kinetics as a function of both the fully modified and unmodified regressed rate data. Using the proposed kinetic model, the conversion, vinyl structure, and heterogeneity index of polymers produced for a series of continuous runs were successfully predicted. The model was used to simulate several process configurations.