Spectroscopic Signature and Structure of the Active Sites in Ziegler–Natta Polymerization Catalysts Revealed by Electron Paramagnetic Resonance
Anton Ashuiev, Matthieu Humbert, Sébastien Norsic, Jan Blahut, David Gajan, Keith Searles, Daniel Klose, Anne Lesage, Guido Pintacuda, Jean Raynaud, Vincent Monteil, Christophe Copéret, Gunnar Jeschke
Abstract
Despite decades of extensive studies, the atomic-scale structure of the active sites in heterogeneous Ziegler–Natta (ZN) catalysts, one of the most important processes of the chemical industry, remains elusive and a matter of debate. In the present work, the structure of active sites of ZN catalysts in the absence of ethylene, referred to as dormant active sites, is elucidated from magnetic resonance experiments carried out on samples reacted with increasing amounts of BCl3 so as to enhance the concentration of active sites and observe clear spectroscopic signatures. Using electron paramagnetic resonance (EPR) and NMR spectroscopies, in particular 2D HYSCORE experiments complemented by density functional theory (DFT) calculations, we show that the activated ZN catalysts contain bimetallic alkyl-Ti(III),Al species whose amount is directly linked to the polymerization activity of MgCl2-supported Ziegler–Natta catalysts. This connects those spectroscopic signatures to the active species formed in the presence of ethylene and enables us to propose an ethylene polymerization mechanism on the observed bimetallic alkyl-Ti(III),Al species based on DFT computations.