In‐Depth Investigation of Ethylene Solution Polymerization Kinetics With rac‐Et(Ind)2ZrCl2/MAO

Abstract The kinetics of ethylene polymerization with rac‐Et(Ind)2ZrCl2/methylaluminoxane (MAO) in a semibatch solution reactor are investigated. The effects of ethylene concentration, polymerization temperature, and MAO concentration are studied to determine the polymerization and chain‐transfer rate constants, including the activation energies for the main polymerization steps. The ethylene polymerization kinetics with rac‐Et(Ind)2ZrCl2/MAO are first order with respect to the ethylene concentration. Catalyst deactivation also follows first‐order kinetics. Chain transfer to the monomer is the dominant chain‐transfer reaction in this system; transfer to MAO also happens to a lesser extent, but β‐hydride elimination is negligible for the conditions investigated in this study.