Interaction of different poisons with MgCl2/TiCl4 based Ziegler-Natta catalysts

Adsorption of different poison molecules on activated MgCl2 is investigated within DFT using a cluster model of the MgCl2 surface with (MgCl2)(16) formula containing four 4-coordinated and eight 5-coordinated Mg atoms as (110) and (104) surfaces, respectively. Studied poison molecules are chosen as possible impurities in hydrocarbon solvents and monomer feeds and contain water, hydrogensulfide, carbondioxide, molecular oxygen and methanol. First, adsorption of 1-4 molecules of different poisons to the (104) and (110) lateral cuts of MgCl2, as well as their adsorption on [MgCl2]/TiCl2 Et active center and AlEt3 cocatalyst is considered. Results reveal that poisons strongly stabilize both crystal surfaces, mostly Ti active center relative to the unpoisoned solid. Second, energy barrier (E-TS) for ethylene insertion in the presence of different poisons located on the first and second Mg atom relative to the active Ti is calculated. While poison molecule located on the second Mg does not change E-TS, coordination of it into the first Mg atom increases E-TS by 0.9-1.2 kcal mol(-1). In the last part of this manuscript, the stereoselective behavior of active Ti species, with and without poison molecules and external electron donor, is fully explored. (C) 2016 Elsevier B.V. All rights reserved.