Ethylene Polymerization via Zirconocene Catalysts and Organoboron Activators: An Experimental and Kinetic Modeling Study

Forty years after the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when “conventional” alkylaluminum activators not used. Herein, we systematically investigated synthesis polyethylene (PE) via three different zirconocene with alkyl substituents, activated organoboron compounds. The polymerization behavior, as well properties materials, were evaluated. results demonstrate highest catalytic activity is shown by bis(cyclopentadienyl)dimethylzirconium trityl tetra(pentafluorophenyl)borate. Additionally, it was found toluene optimum solvent for these systems and at reaction conditions. Moreover, to validate our experimental results, a comprehensive mathematical model developed on basis thermodynamic kinetic principles. concentration ethylene transferred phase (toluene) in liquid–vapor equilibrium (LVE) system estimated based Duhem’s theorem. Arrhenius expressions rate constants proposed mechanism model, which fitted least-square optimization procedure molecular weight averages method moments. simulations coordination suggest presence two types active sites, principally low temperatures, reactivation deactivated sites boron-based activator. However, effect temperature step clear; deeper understanding designed experiments required.