High-throughput DFT investigation of chain initiation and propagation rates in single-site olefin polymerization catalysts containing mixed cyclopentadienyl/aryloxide ligation

CATL 31

Thomas A. Manz, tmanz@purdue.edu1, Kendall T. Thomson1, James M. Caruthers, caruther@ecn.purdue.edu1, W. Nicholas Delgass, delgass@ecn.purdue.edu1, Mahdi M. Abu-Omar, mabuomar@purdue.edu2, Khamphee Phomphrai, kphomphr@purdue.edu2, Shalini Sharma, sharma5@purdue.edu2, Grigori Medvedev1, Krista A. Novstrup1, and Andrew E. Fenwick2. (1) School of Chemical Engineering, Purdue University, Forney Hall of Chemical Engineering, 480 Stadium Mall Drive, West Lafayette, IN 47907, (2) Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IN 47907-2084
Over thirty Ti and Zr single-site olefin polymerization catalysts containing mixed cyclopentadienyl/aryloxide ligation were studied using density functional theory and compared to experimental data in order to develop structure-activity correlations. For some of the catalysts, transition state analysis for catalyst activation, chain initiation, chain propagation, chain transfer, chain termination, and catalyst deactivation steps was performed. For all of the catalysts, a series of chemical descriptors based on ground state energies and geometries was used to better understand reactivity trends for different catalytic steps. We investigated the effects of solvent, ligand structure, counterion, and metal on the reaction rates, polymer molecular weights, and catalyst descriptors. For some catalysts, the rate of chain initiation was approximately one thousand times slower than chain propagation. For other catalysts, the rates of chain initiation and propagation were approximately equal. A model was developed to explain these results.