β‐Myrcene Coordination Polymerization: Experimental and Kinetic Modeling Study

The present work presents phenomenological models to describe the coordination polymerization of β‐myrcene using the Ziegler–Natta catalyst system composed by neodymium versatate (NdV3), diisobutylaluminum hydride (DIBAH), and dimethyldichlorosilane. The kinetic parameters required to simulate the reactions are estimated, and the amount of DIBAH used as a chain transfer agent (CTA) is obtained by a data reconciliation strategy since it can participate in side reactions. Several experiments are performed at different conditions to evaluate the impact of key operation variables on the control of monomer conversion and average molar masses. It is shown that the initial NdV3, β‐myrcene, and DIBAH concentrations exert strong influences on the course of the polymerization. The kinetic mechanism of Coordinative Chain Transfer Polymerization (CCTP) fits well with the data of final average molar masses and monomer conversion, while the dynamic trajectories of these variables are fitted better by kinetic mechanisms of more conventional coordination polymerizations, considering site deactivation and termination by chain transfer. In all cases, the proposed models are able to predict the experimental data well after successful parameter estimation and reconciliation of CTA concentrations, indicating that the kinetic mechanism can be characterized by different kinetic regimes. The β‐myrcene polymerization can occur in a coordinative chain transfer polymerization regime or typical coordination polymerization, depending on the experimental conditions. This article develops mechanistic models to describe these polymerizations performed using a ternary Ziegler‐Natta catalyst system. Kinetic parameters are estimated, also estimating the amount of aluminum used as a chain transfer agent through a standard data reconciliation procedure.